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Pur(e) Fascination...

Whichever way you look at it, with innovative technologies and the widest range of equipment for fascinating Polyurethane products all over the world, Hennecke has been laying the foundation for superior product quality and efficient use of raw materials in all areas of application for over 65 years.

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The golden calf…

Once upon a time a poor farmer had a calf that he was trying to nourish and grow as best as he could. He was living quite happily in his little hut watching the calf thrive and prosper, it was truly a delight. They were living a basic but a happy and sustainable life. (In fairy tales cows don’t produce the GWP methane gas…)

But as always in fairy tales, evil is waiting just around the corner.

It was on a beautiful summer weekend, when some city boys decided to make a countryside tour. They drove in big shiny cars, drinking a lot of champagne, praising and cheering themselves as they had taken some investors for a ride during the week.

So it happened that they passed the little hut with the farmer and his calf.

When they saw the calf one of them became very excited shouting…. “What a great ‘steak(e)’ that could be! It would perfectly complement the Lafite Rothschild that I found in the cellar of the guy who jumped out of his window during the last crash.” (At that times window jumping was quite a common and socially accepted but not very healthy sport in certain circles.)

The others celebrated him like a hero for his wonderful idea and started to convince the farmer that it would be a great thing to have partners in growing the calf. “We will give you enough money to buy the bush”, they promised.

At the beginning, the calf was growing fit and strong, eating rich and nutritious grass that the poor farmer could not afford in the past. But what the city boys didn’t say, was that on the way home they had already started betting on how fast the cow would grow and how big the ‘st(e)akes’ would be. And they found more and more people at the roadside to place a bet on the cow’s growth rate.

But as I said, everything was fine at the beginning and politicians and self-proclaimed cow experts were dancing around the calf, rating it AAA and giving sound interviews to the press. There was a collective mutual backslapping across the whole country so that chiropractics also had a really good business.

But of course the inevitable happened. Soon the city boys were not satisfied anymore and pumped more and more green bucks (that have been freshly printed by the Fed (Fed comes from feeding and not from Federal as simple minded might think) and given to them at no interest rate) into the cow enterprise as the growth rate didn’t meet their expectations. They convinced the farmer not to listen to the vet, who said that the cow was grown up now and would not grow anymore, but to consultants who didn’t have the faintest notion of cow breeding and to a nutrition manager who never had worked on a farm but had a good name as he had ruined a couple of companies already and made a lot of people redundant.

But suddenly and unexpectedly, to all experts, one morning there was a big bang shaking the country to the core. The triple A cow exploded due to overfeeding leaving the land devastated...

But how did the story move on?

Oh well, the politicians went on their well deserved holiday, the consultants collected the bones and made some nice necklaces for their wives, the manager already had a new contract as a proven cow expert at a TV station explaining that he knew before what was going to happen, and the city boys just said “Oups” turned around and finished the bottle of Lafite Rothschild without a steak. Only the farmer stood aside and thought to himself: “Sometimes I have the feeling there are more intelligent life-forms living in the puddle in front of my hut than in the whole city.”

And if they didn’t jump out of the window they will start the same game tomorrow again...

At the moment I would love to invest in diving boards and provide them to some of those guys for free…

Anybody joining?

Best regards Frank A. Gupta

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NO. 4 · AuGust/sEPtEMBER 2011

Utech.Asia.2011.preview Page.211

CONTENT Dow.and.Saip.customers.. inaugurate.ce|de|pa Page.214

Editorial............................................................................................ 191 A.study.in.sustainable.living Page.220

News.

Industry.news................................................................................. 194 People......................................................................................... 199 Reviews. ...................................................................................... 200.

Events......................................................................................... 202

CPI.Polyurethanes.2011.Technical.Conference.preview...................... 206 Utech.Asia.2011.preview................................................................... 211 Dow.and.Saip.customers.inaugurate.ce|de|pa.................................... 214 Walk.the.Talk.–.2nd.Generation............................................................ 216 Honeywell.launches.fourth.generation.. high.performance,.LGWP.blowing.agent............................................. 217 A.study.in.sustainable.living............................................................... 220 Insulating.prefabricated.houses.with.PU.sandwich.elements................ 222 Bayfomox.spray.foam.–. a.flame-retardant...

Page.224

SWD.Shanghai.completes.. final.phase.of.Oceanic.. polyurea.coating.project Page.230

O. Mauerer

Bayfomox.spray.foam.–.a.flame-retardant.. polyurethane.system.with.remarkable.properties................................ 224 SWD.Shanghai.completes.final.phase.of..

Oceanic.polyurea.coating.project....................................................... 230 Emery.Oleochemicals.uses.170.year.old.legacy.. to.develop.renewable.ester.polyols.................................................... 232 R. Irnich

Sustainable.production.of.PU.synthetic.leather................................... 234 J. Kang, G. Erdodi, J. P. Kennedy

A.new.class.of.TPEs:.Melt.processible.polyureas................................. 238 B. W. Naber, G. Behrendt

Recycling.flexible.foam.PUR.–.part.4.–.thermal.recovery.................... 244 Suppliers.list..................................................................................... 249 Publication.information.&.contacts..................................................... 254 Recycling.flexible.foam.PUR.–.. part.4.–.thermal.recovery 192 Page.244

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

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This new system features specially formulated polyurethane foam and a patented vacuum process that together enable fast, effective and consistent filling of appliance cabinets – without extra material. in addition, the technology enables up to 50 percent faster demold times compared to standard processes. paScal technology represents a real breakthrough for manufacturers, enhancing appliance energy efficiency by as much as 10 percent. and when used in place of standard appliance polyurethane insulation, it may save 8 kg of co2 equivalent emissions per year per unit produced.

Visit www.dowpascal.com today to learn more about how your business can take energy efficiency and productivity to the next level with paScal technology.

193 ®™Trademark of The dow chemical company (“dow”) or an affiliated company of dow

Industry news Dow and Saudi Aramco announce “Sadara” JV Dow and the Saudi Arabian Oil Company (Saudi Aramco) announced on 25 July 2011 that the Boards of Directors of both companies have approved the formation of a 50/50 joint venture, named Sadara Chemical Company, to build and operate a world-scale, fully integrated chemicals complex in Jubail Industrial City, Kingdom of Saudi Arabia. Total investment for the project, including third party investments, will be approximately USD 20 billion.

Comprised of 26 manufacturing units, the complex is said to be one of the world’s largest integrated chemical facilities, and the largest ever built in one single phase. It will possess flexible cracking capabilities and will pro-

duce over 3 million t of chemical products and performance plastics such as isocyanates, polyether polyols, propylene oxide, propylene glycol, elastomers, LLDPE, LDPE, glycol ethers, and amines.

Sadara will have responsibility for product marketing within a local zone of eight countries. Dow will market and sell on behalf of Sadara to all countries outside of the Middle East zone.

The first production units will come on line in the second half of 2015, with all units expected to be up and running in 2016.

Once operational, Sadara is expected to deliver annual revenues of approximately USD 10 bil- online lion.

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Solvay to form JV with Sadara to build HP plant Solvay announced that it has the intention to create a 50/50 joint venture with Sadara Chemical Company for the construction and operation of a hydrogen peroxide plant in Jubail Industrial City, Kingdom of Saudi Arabia.

Scheduled to be operational in the second half of 2015, this plant is intended to supply HP as

a raw material for the manufacture of propylene oxide by Sadara at its world-scale, fully integrated chemicals complex.

Sadara itself is the joint venture of Saudi Arabian Oil Company (Saudi Aramco) and Dow online (see above).

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SKC announces plans to expand PO capacity SKC announced plans to expand its PO capacity to 600 kt by 2016, starting with the first revamping project designed to add a production capacity of 30 kt to

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its current HPPO plant in 2011.

The company plans to complete this revamp by the first half of 2012 and start an additional revamp to add 70 kt by the end of

2012. If the expansion roadmap could be completed on track, SKC might double the production capacity of its HPPO plant from 100 kt to 200 kt by 2013.

SKC also plans to add another HPPO plant by 2016, with a capacity of 200 kt. As such, the company will have a combined production capacity of 600 kt of PO by the end of 2016.

While expanding its PO capacity, SKC will accordingly enlarge its PO downstream production such

as polyol and propylene glycol, and global system houses. By the end of 2016, it aims to secure a production capacity of 400 kt of polyol and 200 kt of PG, in addition to 600 kt of PO. The system houses also could get to its global hubs throughout the US, China and Poland.

In 2008 the Korean company has commissioned in Ulsan the first commercial-scale plant for production of PO by the HPPO process developed by Evonik and Uhde.

Chinese delegation signs license for Evonik-Uhde HPPO process Evonik and representatives of a Chinese delegation led by Governor Wang Rulin of China’s Jilin Province signed an agreement for a non-exclusive license to build and operate an HPPO (hydrogen peroxide to propylene oxide) plant at a site in Jilin, Northeastern China. The license

agreement will allow a yet to be established joint venture between Jilin Shenhua and Jilin North Chemical Company (JNCC) to build a facility for the production of 300,000 t of propylene oxide, which will operate on the basis of a process developed by Uhde and Evonik.

Last year, Evonik posted revenues of over EUR 1 billion in China, Hong Kong and Taiwan where it employs more than 3,500 people.

The company manages its activities in China from Shanghai, where Evonik operates a large R&D centre, a production site of its own, and a multi-user site at SCIP (Shanghai Chemical Industry Park). Over the past years, the company has invested over EUR 300 million in Shanghai. Additional investments are planned in the form of an oleo chemical shared facility and a shared isophorone facility.

BASF to expand MDI site in Yeosu BASF expands the capacity of its Yeosu MDI plant. The expansion will require a total investment of approximately EUR 50 million, shared between BASF and other companies, at Yeosu Industrial Complex. The expansion will take place between 2011 and 2012, and increase MDI capacity by 60,000 t/y to

250,000 t/y. Around 40 new jobs will be created through the expansion. BASF’s Yeosu site was established in 1998 and currently has an annual production capacity of 190,000 t/y of MDI, 160,000 t/y of TDI, and 20,000 t/y of CCD (carbonyl chloride derivatives). The site employs 280 people and was

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designated a foreign investment area in 2000.

According to BASF’s Asia Pacific Strategy 2020, the company

plans to invest EUR 2.3 billion in the Asia Pacific region between 2011 and 2015.

Kumho Mitsui expanding MDI capacity Kumho Mitsui Chemicals (KMCI), a joint venture of Japan Mitsui Polyurethane and Korea Kumho Chemicals, has increased its Yeosu-based MDI facilities. The expansion is expected to be completed in the

second part of 2012. After completion the company’s MDI capacity in South Korea will increase to 200 kt/y from a current 150 kt/y. online

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BMS expands R & D center in Shanghai In June Bayer MaterialScience held a ground-breaking ceremony for the third phase of the expansion of its Polymer Research & Development Center in Shanghai. The PRDC is scheduled to be operational by the second half of

2012. The expansion is part of a EUR 1 billion investment plan announced in December 2010.

China is the largest market in the Asia/Pacific region and the third largest single market for Bayer globally.

BASF Korea and Daelim Industrial cooperate on insulation solutions for outer wall BASF Korea and Daelim Industrial announced plans to cooperate in the field of Exterior Insulation Finishing Systems (EIFS).

The technical cooperation includes the establishment of a joint research network between the two companies as well as research on design methods for insulation systems.

In the European housing market, BASF widely uses self-developed wet-processed EIFS – which are composed of the Senergy system, mostly made up of Neopor insulation, air-barrier spray urethane insulation Wallt i t e system, and more. online

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TSE opens manufacturing site in Changzhou TSE Industries, Inc., Clearwater, FL, USA, has opened the doors to its new manufacturing facility Changzhou TSE Rubber & Plastic Products Mfg. Co., Ltd. located in Changzhou in the Jiangsu province just outside of Shanghai.

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TSE Industries, Inc. North American Engineered Polymers Division Vice-President Frank Cucchiara heads the new facility, which will expand compression and injection rubber moulding, grinding and rubber-to-metal/ rubber-to-plastic bonding opera-

tions. Longer term goals will include development of a custom plastics machine shop into the region. Other divisions that will continue to be supported from headquarters in Clearwater, FL, include the CASE Division (reactive hot melt adhe-

sives, two-part polyurethanes and toll manufacturing) as well as Millathane millable urethane, and TSE-Okulen Americas, LLC, which produces UHMW (ultra h i g h m o l e c u l a r online weight) plastic sheet.

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Brenntag to acquire Chinese distributor Zhong Yung Brenntag announced that it has signed a purchase agreement to acquire 100 % of Zhong Yung (International) Chemical Ltd. Deal closing for the first tranche is expected in the third quarter of this year. Brenntag will hold a majority stake of 51 % and will acquire the remaining stake in 2016.

Zhong Yung is a major chemical distributor in China with about 2,000 customers and more than 100 suppliers. It serves solventapplied industries such as paint and coatings, adhesives, printing inks, electronics, and automotive with a large variety of solvent products. It is estimated to generate sales of EUR 255 million in 2011.

Lapolla achieves EU approval and CE marking for SPF Lapolla Industries, Inc., the Houston-based manufacturer and supplier of spray foam insulation, cool roof coatings and equipment, continues to expand its global reach by achieving European Technical Approval and CE Marking for its low density open cell spray foam insulation Foam-LOK FL 500. Lapolla said that this latest achievement signals the company’s intention to aggressively develop its international distribution channels in the near future.

A European Technical Approval (ETA) for a construction product is a favourable technical assessment of its fitness for an intended

The

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online

use. In conjunction with an Attestation of Conformity (AC) procedure, ETAs allow manufacturers to place CE marking on their products, this is a key indicator of a product’s compliance with EU legislation and enables the free movement of products within the European market. By affixing the CE marking on a product, a manufacturer is declaring conformity with all of the legal requirements to achieve CE marking and therefore ensuring validity for that product to be sold throughout the European Economic online Area.

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PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

Repi opens company in Russia The Italian company Repi S. p. A. has recently opened its own company in Moscow, OOO Repi, following 12 years of work on the Russian market, the last five years of which through its own representative office. According to Repi, the growing importance of the Russian market led to the decision to open the own Russian company. It offers full technical support, including colouration advice as well as just-in-time deliveries from the Moscow warehouse.

Repi says the new company holds a leading position in Russia for the supply of colourants and additives for PET preforms. It is also promoting its basic colourant technology for the extrusion of PVC profiles and panels. Other areas of growth cover colours for bi-component polyurethanes, epoxy resins, polyurea – as well as extrusion and calendering of sheets, rotational moulding of PVC, and injection moulding of technically complex polymers, says Repi.

Part of the OOO Repi team

Repi offers liquid colourants and additives for plastics and polyurethanes, own dosing units for the use of its products, and technical service worldwide. The main fields of application for its products are packaging, automotive, furniture, construction, and footwear. The company’s headquarters, production, and R&D centre are located near Milan, in northern Italy. In addition, it has subsidiaries in the USA and Russia. According to Repi, 75 % of its total production is exported into 60 countries.

PDA Europe continues to focus on promotion of polyurea Recently the PDA North America has adopted changes in its mission and will include basically all isocyanate-based coating technologies in the organisation and thus move away from the promotion of polyurea only. On a meeting of the Board of Directors of PDA Europe, it was decided that the PDA Europe will continue to be a solely polyurea-oriented

trade association. “We still see a demand in Europe for a specifically polyurea-oriented organisation which promotes the benefits of the polyurea technology and its manifold application areas. In our geographical region we still have tasks to fulfill to get this, unique technology, widely established. There are lots of opportunities in the elastomeric coating

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market, and there is a need to inform and to cooperate with this industry and its specifying organisations. In addition there is also a need to establish polyurea as a new material in the manifold European and national regulations and norms, a prerequisite to obtain the required certificates for the diverse applications�,

stated PDA Europe President Stephan Rindfleisch.

PDA Europe confirmed that unless the majority of its members will propose a change in the mission, to open up for other isocyanate-based technologies, it will remain a trade association focusing solely on the polyurea technology.

The Polyurea Development Association Europe (PDA Europe) is the official trade association for the European polyurea industry. Registered as an official, international not-for-profit association under Belgian law, PDA Europe promotes the highest possible standards for polyurea.

Agrol polyols approved to use USDA biobased product label Agrol and Agrol Diamond, manufactured by BioBased Technologies, Springdale, AR, USA, have been approved to use the US Department of Agriculture certified biobased product label.

The label indicates that the products have been independently certified to meet the USDA Bio-

Preferred programme standards for bio-based content.

The products are soy-based polyols for use in a variety of PU products including spray foam insulation, carpet padding, and automotive seat foam. The company said that Agrol 2.0 – 7.0 has a 99 % bio-based carbon con-

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tent, and Agrol Diamond a 86 % bio-based carbon content according to ASTM D6866.

The USDA certified biobased product label is the second component in the two-part USDA BioPreferred programme. The first part of the

programme established minimum bio-content standards for a variety of product categories, and then created an online catalog of more than 5,100 qualified products for preferred purchasing by government agencies.

Honeywell to invest USD 33 million in Louisiana facility Honeywell announced that it will invest USD 33 million in its Baton Rouge, LA, USA, manufacturing facility. This investment will provide the site with the ability to produce the company’s new lowglobal-warming-potential (GWP) blowing agent and propellant HFO-1234ze on a commercial scale. Production of HFO-1234ze at the facility is scheduled to begin in late 2013.

HFO-1234ze is non-flammable, non-ozone depleting and has a GWP of 6. Earlier this year, the product was recognised at the Paris Aerosol Forum as the best new technical product innovation.

The prize was awarded by an independent jury of aerosol exp e r t s re p re s e n t i n g brand owners, packaging manufacturers, online and the media.

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Sanitized starts direct commercialisation of its products The Swiss company Sanitized AG has expanded its services for the growing number of users of antimicrobials in the plastics industry. The company will now follow a new strategy of direct commercialisation after having partnered with Clariant over the last years.

Furthermore, the company has launched a new product for PU foam and coatings. Sanitized TPL 27-40 offers a good antibacterial effect in combination with protection against fungal activity. In addition, it provides an anti-dust mites effect and it is wash-resistant.

Call for papers: Blowing Agents & Foaming Processes 2012 iSmithers and sister company Smithers Rapra invite to the the 14th international Blowing Agents and Foaming Processes conference from 8 – 9 May 2012 in Berlin, Germany. The established event is dedicated to blowing agents in foamed plastics, polyurethane, and rubber. The organisers are currently recruiting speak-

ers for this event and have issued a call for papers. Deadline for the submission of abstracts is 28 October 2011.

Contact: iSmithers ¡ Helen Charlesworth Tel. +44 1939 250383 Fax +44 1939 251118 E-mail hcharlesworth@ismithers.net Internet www.ismithers.net

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

People Kissam new CEO of Albemarle Luther C. Kissam has been elected as new CEO of Albemarle Corporation. He joined the Baton Rouge, LA, based US company in September 2003. Prior to that he was with Merisant and Mon-

santo. On 1 September 2011 Kissam will take over the CEO chair from Mark C. Rohr who will continue as executive Chairman of the Albemarle Board of Directors.

Multi-faceted: New Strategic Marketing Director for Dow Performance Materials Dow Chemical has named Carlos Silva Lopes as Strategic

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For high performance PUR at competitive prices its tough to beat Solkane® 365mfc. Solkane® 365mfc gives you the best lambda values of any ODP zero foaming agent. Ask for our latest ecoefficiency studies which impressively demonstrate how Solkane® 365mfc brings out the best in your PUR/PIR products – economically and ecologically!

Marketing Director for its Performance Materials business, which includes the speciality companies Angus Chemical Company and Acima Specialty Chemicals. In this role, he will lead all global marketing activities for a number of diverse markets. Silva Lopes joined Dow in 1990. Most recently, he served as the Global Marketing Director for Dow Fabric & Surface Care, a business unit of Dow Home & online Personal Care.

Safe handling With a boiling point of 40 °C, Solkane® 365mfc is a true liquid. This guarantees easy handling, and safe and cost effective packaging.

Top team Solkane® 365mfc is the perfect team player: with Solvay’s own R 365/227 range of non-flammable blends, or other combinations with HFCs and even hydrocarbons – the choices are almost unlimited.

Running Solkane® 365mfc in your system maximizes your insulating performance and minimizes raw material costs. Solkane® 365mfc in your team puts you in a win-win situation.

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Obituary for Dr. John Timberlake working with Fomo, Azon, and Union Carbide where he played a significant role bringing products to market.

Solvay (Shanghai) Co. Ltd. Building 7, No. 899 Zu Chong Zhi Road Zhangjiang High-tech Park Shanghai 201203, China Phone +86 21 50805080 Fax +86 21 50805376

Solvay Fluor GmbH Postfach 220 30002 Hannover, Germany Phone +49 511 857-2444 Fax +49 511 857-2166 foamingagents@solvay.com www.solvay-fluor.com

Solvay Fluor Dr. John Timberlake

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

www.ahlersheinel.de

Dr. John Timberlake, Technical Director of Foam Supplies, Inc. (FSI) since April 2005, has died on 9 March 2011 at the age of 63. Timberlake graduated from North Carolina State University with Honours in Chemistry, and later attained his Ph.D. in Organic Chemistry in 1976. His work at FSI focused on insulation in buildings and appliances. He also worked with one component foams, thermal breaks, caulks and sealants. He had a long career in polyurethane, formerly

Solvay Fluor Korea CO., LTD 5th Fl. Donghwa Bldg. 58-7 Seosomun-Dong, Jung-Gu Seoul 100-736, Korea Phone +82 2 757 5353 Fax +82 2 756 0354

A Group active in Chemistry The use of Solkane®365mfc and of blends containing Solkane®365mfc might fall within the scope of U.S. patent no. 5,496,866. The following must be noted regarding the USA (until March 5, 2013): (1) Solkane®365mfc cannot be used in the USA, by itself or in a blend, as a blowing agent to foam a plastic based on an isocyanate to form plastic foam compositions; (2) Solkane®365mfc and blends containing Solkane®365mfc must not be made, used, offered for sale, or sold in the USA, or imported into the USA, for such blowing uses; and (3) closed cell plastic foam compositions prepared by foaming a plastic material based on isocyanate in the presence of a propellant comprising Solkane®365mfc and/or a blend containing Solkane®365mfc, cannot be made, used, offered for sale, or sold, within the USA, or imported into the USA. To do so can result in a claim of patent infringement under U.S. patent no. 5,496,866. Solvay will not sell Solkane® 365mfc or blends containing Solkane®365mfc to any purchaser intending to use the product accordingly. For addional information and details please visit our webside: www.solvay-fluor.com.

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AkzoNobel CEO Wijers to leave 2012 Hans Wijers, 60, CEO of AkzoNobel, has decided to step down with effect from the Annual General Meeting (AGM) 2012. Ton Büchner, 45, was elected as new CEO pending AGM approval, with effect from the AGM 2012.

Büchner is currently President and CEO of Swiss Sulzer AG. Wijers was appointed CEO of Akzo Nobel in May 2003. He previously pursued a career as minister for economics in the Netherlands and within management consultancy. In his first few years, he improved the pipeline of the

Pharma business, focused the Chemicals businesses and grew Coatings. He led the transformation of the company by divesting its pharmaceuticals operations and acquiring ICI, effectively creating today’s AkzoNobel.

Büchner has been CEO of Sulzer AG since 2007. He joined the Swiss company in 1994. He started his professional career as an offshore oil and gas construction engineer with Allseas Engineering in Europe and worked for AkerKvaener throughout South East Asia for several years.

Senior management changes at BMS Effective 1 July 2011, Peter Vanacker has been appointed to the Executive Committee position of Head of the newly established function Global Industrial Marketing at Bayer MaterialScience.

This function will chair both the Global Marketing and Innovation communities at BMS. In addition, he will lead the company’s development business activities in Functional Films and Carbon Nanotubes, amongst others.

At the same time, Dr. Joachim Wolff succeeds Vanacker as Head of the Polyurethanes business unit, while Daniel Meyer

joins the Executive Committee and succeeds Wolff as Head of the Coatings, Adhesives and Specialties business unit. Meyer was previously Head of Marketing and Business Development within this business unit in the Asia Pacific Region.

Furthermore, Michael Bernhardt, Wolfgang Miebach and Richard Northcote have joined the Executive Committee on 1 July 2011 in their positions as Heads of Human Resources, Corporate Development, and Communications and Public Affairs, respectively.

FXI names new President and CEO John Cowles has been appointed President and Chief Executive Officer of FXI and a member of the Board of Directors, effective immediately. He succeeds Jack Johnson, who is retiring after six years and two tours of duty but will remain on the Board as Non-Executive Chairman. Most recently, Cowles was CEO of

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Touchstone Wireless. Prior, he was President at George Weston Bakeries of Horsham, PA, USA. Cowles also served as Executive Vice President and General Manager for Kraft Foods. He also worked for nine years at Campbell Soup Company. He began his career at Booz, Allen & Hamilton, Inc.

Reviews 2010 End-Use Market Survey on the Polyurethanes Industry Center for the Polyurethanes Industry, Washington, DC, UsA, 2011, 300 p., UsD 1,000 – 2,000 hardcopy, UsD 2,500 – 5,000 electronic copy incl. Excel data charts The Center for the Polyurethanes Industry (CPI) of the American Chemistry Council has announced that the 2010 End-Use Market Survey on the Polyurethanes Industry in the United States, Canada and Mexico is now available to order. Developed by IAL Consultants on behalf of the CPI, the study provides a breakdown of PU production by type and by major end-use market for each country. In addition, four-year data trends are presented along with discussions of the market status in 2010. With the economic transitions in some markets over the past two years, additional data and commentary

will be provided for 2009 and 2010. The study provides commentary on the drivers for PU and how it can make an effective contribution to our daily lives. Additional data also will be provided to help describe the NAFTA market and discussing the position of PU to other materials in the marketplace such as insulation, flooring underlay and the bedding market. The latest available industry data for the end-use markets (automotive, refrigeration, furniture, bedding, building and construction) also are included.

Discounts are available for CPI members who place their order by 1 September 2011.

Polyurethane Elastomers Cristina Prisacariu, springer-Verlag, Wien, 2011, 260 p., hardcover, EUr 106.95, IsbN 978-3-7091-0513-9 The book Polyurethane Elastomers – From Morphology to Mechanical Aspects includes a comprehensive account of the physical/mechanical behaviour of polyurethanes elastomers, films and blends of variable crystallinity. Aspects covered include the elasticity and inelasticity of amorphous to crystalline polyurethanes, in relation to their sensitivity to chemical and physical structure.

A study is made of how aspects of the constitutive responses of polyurethanes vary with composition: the polyaddition procedure, the hard segment, soft segment and chain extender (diols and diamines) are varied systematically in a large number of systems of model and novel crosslinked and thermoplastic polyurethanes.

Results will be related to: microstructural changes, on the basis

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

cool performance

New blowing agent talent discovered.

When Honeywell’s Solstice Blowing Agent takes the stage in 2013, it will create an overnight sensation. Taking inspiration from the many qualities that made HFC-245fa famous, this new high-performing molecule promises instant stardom. Its superior insulation performance and GWP of only 7 blows past the competition. Whether you’re focused on refrigerator, spray foam, panel or any number of other applications, our Solstice Blowing Agent’s versatility will be music to your ears.

It hasn’t gone commercial yet but, when it does, you’ll want to be ready.

For more information call 973-455-4334.

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

© 2011 Honeywell International Inc. All rights reserved.

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of evidence from x-ray scattering (SAXS and WAXS), and also dynamic mechanical analyses (DMA), differential scanning calorimetry (DSC) and IR dichroism.

Inelastic effects will be investigated also by including quantitative correlations between the magnitude of the Mullins effect and the fractional energy dissipation by hysteresis under cyclic straining, giving common relations approached by all the materials studied. A major structural feature explored is the relationship between the nature of the hard segment (crystallising or not) and that of the soft segments. Crystallinity has been sometimes observed in the commercial polyurethanes hard phase but this is usually limited

to only a few percent for most hard segment structures when solidified from the melt. One particular diisocyanate, 4,4’-dibenzyl diisocyanate (DBDI) that, in the presence of suitable chain extenders (diols or diamines), gives rise to significant degrees of crystallinity [i-iii] and this is included in the present work. Understanding the reaction pathways involved, in resolving the subtle morphological evolution at the nanometre level, and capturing mathematically the complex, large-deformation non-linear viscoelastic mechanical behaviour are assumed to bring new important insights in the world basic research in polyurethanes and towards applied industrial research in this area.

North American Market Report for Adhesives and Sealants the Adhesive and sealant Council (AsC), bethesda, MD, UsA, 2011, UsD 630.00 for AsC members, UsD 945.00 for non-members The Adhesive and Sealant Council (ASC) has released the North American Market Report (NAMR) for Adhesives and Sealants, a report published every three years, and which covers the 2010 – 2013 time period. The report was produced on behalf of the ASC by DPNA International, a market analyst and research firm that is also an affiliate member of the council. The NAMR covers market size and scope for both adhesives and sealants, and includes forecasting and trends analysis. According to the report, the global adhesives and sealants market is estimated at

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USD 40.5 billion in sales, with 3.3 % annual growth rate through 2013, while the North American market is estimated at USD 11.1 billion, with 2.2 % annual growth rate. Most markets are expected to grow, with emphasis on end use categories including packaging, building and construction, and footwear, while transportation will have slower growth. The full report also includes a macro assessment of Western Europe, the Far East, Latin America and the rest of the world. The NAMR is harmonised with Feica’s European market report.

The report includes sections detailing the breakdown by market segment, including global de-

mand by market segment as follows: paperboard/packaging (33 %), building/construction (18 %), woodworking (11 %), assembly (10 %), sealants (10 %), transportation (7 %), footwear (4 %), consumer/DIY (4 %), and other (3 %). The report outlines which technologies are leveraged in the marketplace, including: water borne (50 %), solvent borne (16 %), reactive (15 %), hot melt (14 %), and other (5 %).

It describes global demand by polymer type, including: vinyl (31 %), acrylic (16 %), rubber (13 %), other (11 %), polyurethane (8 %), block copolymers (7 %), epoxy (5 %), natural products (5 %), and silicone (4 %).

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Events Applas 2011

The 12th Asian-Pacific international plastics and rubber industry exhibition, Applas 2011, is set to take place from 6 – 9 September 2011 in the New International Expo Centre in Shanghai, China. According to the organiser, Applas Co., Ltd., the event is one of the most influential trading platforms for the plastics and rubber industry in China.

Contact: Applas Co., Ltd. · Edwin Sun Tel. +86 10 66039-043, -351 · Fax +86 10 66067681 E-mail sunlei@applas.com · Internet www.applas.com.cn

American Coatings Show and Conference 2012 The American Coatings Conference will take place from 7 – 9 May 2012 in conjunction with the American Coatings Show, to be held 8 – 10 May 2012, in Indianapolis, IN, USA. The organisers, the American Coatings Association (ACA) and Vincentz Network, are calling for papers to be presented at the conference.

Presentations are invited on latest research results that highlight advancements in raw materials and formulations, printing inks, adhe-

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

We create better durability.

Together.

At Huntsman Polyurethanes, we believe that working in true collaboration with customers is the only way to solve complex problems and find the solutions that will deliver real innovation.

So, we strive with a passion and determination to build the deep understanding of our customers that’s required to get to the heart of their needs and establish lasting partnerships.

When it comes to creating better durability in critical structures such as bridges, we’ll work with you to produce tailored MDI-based coatings that provide enhanced structural integrity and protection against corrosion. Combine our knowledge of coatings with your expertise, and we’ll create better bridges… together.

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

www.huntsman.com/pu

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The World‘s Top Trade Fair for Injection Moulders Plastic Technologies - Made by Fakuma sives and sealants, laboratory methods, laboratory equipment and process equipment. Deadline for the submission of papers is 30. September 2011.

Contact: Vincentz Network · Matthias Janz Tel. +49 511 9910-273 · Fax +49 511 9910-279 E-mail matthias.janz@vincentz.net Internet www.american-coatings-show.com

Understanding Polyurethanes – Formulations and Applications 21st FAKUMA – The International Trade Fair for Plastics Processing Exhibition Accents: • injection moulding machines • welding machines • Measuring machines • extruders and and test instruments extrusion plants • recycling • Processing machines • auxiliary equipment • machines and equipment • Raw materials and auxiliaries for preprocessing • Semi-finished • Machining centres and and finished goods surface finishing machine • moulding tools parts • blow moulding machines and components • presses • services

18 – 22 Oct.

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The seminar Understanding Polyurethanes – Formulations and Applications is held once every year at Smithers Rapra in Shawbury, Shrewsbury, Shropshire, UK, and provides an overview of polyurethane formulations and processing technologies, applications and markets in Western Europe and the USA. The modular programme structure allows delegates whose interest lies in a particular production sector to attend for that day only or for any combination of days.

The seminar will take place on 4 – 6 October 2011.

Contact: Smithers Rapra · Gill Tunnicliffe Tel. +44 1939 250383 · Fax +44 1939 251118 E-mail gtunnicliffe@ismithers.net

+

online

Internet www.understandingpolyurethanes.com

FSK Polyurethanes Conference 2011

Exhibition Centre FRIEDRICHSHAFEN w w w.f a k u m a - m e s s e.d e

The German trade association for foamed plastics and polyurethanes (Fachverband Schaumkunststoffe und Polyurethane e. V. – FSK) is organising its annual Polyurethanes Conference in cooperation with Volkswagen AG from 6 – 7 October 2011 in Wolfsburg, Germany. The programme includes 19 technical lectures and a factory visit at VW. All lectures will be held in German with simultaneous translation to English.

Organizer:

Contact: Fachverband Schaumkunststoffe und Polyurethane e. V. Tel. +49 69 2992070 · Fax +49 69 29920711 E-mail fsk@fsk-vsv.de · Internet www.fsk-vsv.de

P.E. Schall GmbH & Co. KG Gustav-Werner-Straße 6 · D - 72636 Frickenhausen · Tel. +49 (0) 7025.9206 - 0 Fax +49 (0) 7025.9206 - 620 · fakuma@schall-messen.de · www.schall-messen.de

www.schall-virtuell.de

Location: Messe Friedrichshafen GmbH · Neue Messe 1 · D - 88046 Friedrichshafen

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A comprehensive overview on these and other upcoming events can be found on the internet at www.pu-magazine.com under the heading of

Member of the associations:

events. The listing provides links to the event websites for detailed information and online registration for your convenience.

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

Fakuma 2011

PDA Annual Conference 2012

The 21st Fakuma will again be held in Friedrichshafen, Germany, from 18 – 22 October 2011. According to the organiser P. E. Schall, 1,541 exhibitors from 30 nations and 37,281 visitors attended the 2009 event. The exhibitor list for this year’s event already includes 1,593 companies (as of 8 August 2011). The international trade fair for plastics processing, which always takes place in the “K”-free years, is characterised by a wide range of processing machines and related peripherals, finished products, raw and auxiliary materials, automation solutions, and services. Interesting forums, workshops, and special shows will round out the spectrum of offerings presented at Fakuma 2011.

The Polyurea Development Association (PDA) will host its 2012 Annual Conference from 26 – 29 March 2012 in Orlando, FL, USA. The conference will combine both educational and informational content with an exhibition hall. PDA will offer courses for the applicators, live demonstrations of spray techniques, a keynote speaker, and breakout sessions. Session topics will include state of the industry, innovative coatings projects, and new spray techniques and processes.

Only recently, the PDA has approved an expanded mission and purpose that now not only includes the promotion of polyurea but in general of spray-applied elastomeric technologies as well as enabling adjacent technologies. In addition, the new tagline to be associated with the PDA is “PDA – Association for High Performance Elastomeric Technologies”.

Contact: P. E. Schall GmbH Tel. +49 70 2592060 · Fax +49 70 259206620 E-mail info@schall-messen.de · Internet www.fakuma-messe.de

Contact:

www.pu-magazine.com

Polyurea Development Association (PDA) · Kelly Nemec Tel. +1 816 2210777 · Fax +1 816 4727765 E-mail kelly.nemec@pda-online.org · Internet www.pda-online.org

Take a look on the light side

KraussMaffei is your system partner for fiber-composite processing.

We have what it takes for successful solutions: – High-performance machines and systems – Application-specific processes to suit your product specs and batch size – Our expert input to support your product development and manufacturing

› INJECTION TECHNOLOGY › REACTION PROCESS MACHINERY › EX TRUSION TECHNOLOGY

There’s not much we don’t know about making lightweight components for automotive interiors, structural parts, bodywork and glazing – why not put our know-how to work for your business?

Come and see us at UTECH Asia/PU China, Shanghai-Pudong, September 06–08, 2011, Booth 620

PU MAGAZINE –Technologies VOL. 8, NO. 4GmbH – AUGUst/sEPtEMbEr 2011 KraussMaffei ··· Phone +49 89 8899-0 info@kraussmaffei.com ··· www.kraussmaffei.com

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CPI Polyurethanes 2011 Technical Conference preview

world’s leading futurists helping to transform growth-oriented organisations. Clients have also included the US PGA, NASA, Burger King, Walt Disney and countless Fortune 1,000 organisations.

He has written over 600 articles and participated in more than 3,000 media interviews in which he provides fast, concise insight to the media on topical leading edge issues.

Scientists, engineers, manufacturers, and business leaders from around the world will meet to look into a world of innovation at the upcoming CPI Polyurethanes Technical Conference at Gaylord Opryland Convention Center. This year’s conference, organised by the American Chemistry Council’s Center for the Polyurethanes Industry, will include 62 papers on innovations in polyurethanes used in construction, appliance, automotive, footwear, adhesive, sealant, and elastomer sectors. Along with the 14 technical sessions, the conference will feature a poster session and two issue sessions. The industry reception on Monday, 26 September 2011, 6 – 7.30 pm will provide a networking opportunity for PU professionals. The sponsored refreshments breaks, poster session, and table top exhibits will also provide further networking opportunities. “The ongoing success of the PU industry is directly tied to innovation, and the CPI Technical Conference is the best place for PU professionals to participate in a free exchange of ideas”, said Lee Salamone, Senior Director, CPI. “It is our role as an industry association to ensure conference attendees understand the challenges of today and how we as a group need to evolve to meet future demands of downstream users and other customers.”

Professional Development Program Sunday, 25 September – Tuesday, 27 September During a three day period eight courses relating to PU chemistry, testing, technology,

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and applications will be held alongside the technical conference. The courses are run by industry experts and provide education and training for the complete range of PU professionals. Registration and further details can be found at: www.americanchemistry.com/polyurethane.

Polyurethane Innovation Award This award recognises the key role played by innovation within the PU industry. Presented for the most innovative applications, this aims to reward the efforts and foresight of companies and individuals who have brought new products and technologies to the marketplace.

Opening session Lee Salamone and Tom Feige, conference committee chair of Dow will open the conference at 9.30 am. This year’s keynote presentation will be made by Jim Carroll who will focus on how forward looking strategies and innovation have paved the way for success for many leading companies.

Table top and poster exhibition will open at the end of the opening session. The programme of technical papers commences after lunch at 2 pm.

Appliances/Cold Chain Monday, 26 September, 2 – 5 pm This session will include innovations in both raw materials and processing technology that lead to improvements in cycle times, flowability and insulation performance in domestic appliances and insulation for the cold chain industry.

• Assessment of HBA-2 as Replacement For HCFC Blowing Agents in Rigid Foams for the Cold Chain Industry – Dow, Dow Italia • Post Demold Expansion of Rigid PU Foam – Bayer MaterialScience LLC • PASCAL Dow Patented Technology – A Novel Breakthrough in PU Foaming Technology For Domestic Appliances – Dow Europe, Dow Italia • A New Generation of Surfactants for HC Blown Foams For Domestic Appliances – Momentive Performance Materials • Household Refrigerator: Low GWP Blowing Agent Performance Update – Honeywell

Automotive Monday, 26 September, 2 – 5 pm

Jim Carroll – Keynote speaker Jim Carroll is a graduate of the University of Toronto, an author, columnist, media commentator, and consultant with a focus on linking future trends, creativity and innovation. From a background in financial and professional services, since 1990, he has been providing his services to become one of the

Advances in antioxidants to lower VOCs in flexible moulded foams, improved paint protection and two updates from the Molded Foam Industry Panel will be presented during this session.

• New Antioxidants For Flexible Foams – BASF Corporation • Crosslinked TPU as Automotive Paint Protection Film – Huntsman International LLC

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

Out of passion for detail.

Automotive Solutions. Performance Passion Success Polyurethane – one of the most versatile materials of our time. Even in the most difficult application areas it guarantees an in every detail accurate display, an outstanding image of the surface and contours, enormous freedom of design and also an exceptional haptic and especially matt visual effects. Elastoskin® and Elastollan® for instrument panels and the centre consoles.

BASF Polyurethanes. Everything else is standard.

Further information about Elastoskin: manfred.michl@basf.com, Elastollan: stefan.arenz@basf.com, PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011 www.pu.basf.de/surfaces

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• Challenges With Odor Testing of PU Molded Foams – Molded Foam Industry Panel • Hysteresis Loss – Is it a Viable Flexible Foam Property? – Ron Blair, Molded Foam

Environment, Health & Safety 1 Monday, 26 September, 2 – 5 pm This session will highlight key regulatory trends and include presentations on the EPA Chemical Action Plan, material handling, emergency reponse planning and the CPI compliance assistance programme. Presentations will be made by members of the CPI EHS committee.

• EPA Chemical Action Plan for MDI and TDI • Sensitisation Potential of Low-Monomer Diisocyanate Prepolymers • CPI Regulatory Compliance Assistance Program (RCAP) • Drum Handling and Disposal • Emergency Response Plans Involving PU Materials

Flame Retardants & Combustibility Monday, 26 September, 2 – 5 pm This session comprises of papers describing new FR developments for the construction industry and concludes with a paper focusing on fire safety issues in China’s building industry.

• New Developments in FRs for the PU Industry – Great Lakes Solutions • Flame Retarded Spray Polyurea – Albemarle Corporation • Comparison of Different Phosphorus FRs in Rigid PU Foams – Lanxess Deutschland GmbH, Lanxess Corporation • FR Developments for Rigid Foam Applications – ICL-IP America Inc. • PU Insulation for Buildings and Fire Issues in China – Bayer MaterialScience (China) Co. Ltd.

CASE Tuesday, 27 September, 9 am – 12 pm Papers presented during this session will focus on advances in adhesive technology and coat-

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ings and more specifically on novel products for use in flooring and roofing applications.

• Novel Reactive Hot Melt PU Adhesives – BASF Corporation • New Developments in Aliphatic Polyurea Coatings – Albemarle Corporation • Stainguard on Steroids – Novel Green Sealer for Decorative Concrete Flooring – Bayer MaterialScience LLC • Elastomeric Waterproof Coatings in the Japanese Roof Market – Albemarle Corporation

Construction 1: Advancing the Science of PUR/ PIR Construction Foam Tuesday, 27 September, 9 am – 12 pm Papers will describe how the versatility of rigid PUR and PIR foams can help the construction industry meet new energy efficiency challenges.

• Easing Transitions Between Blowing Agents in PIR Through Proper Surfactant Selection – Evonik Goldschmidt GmbH • Evaluation of Low GWP Blowing Agents in Pour-in-Place Panel Applications – Honeywell • The Benefits of Optimization in Ecomate Blown Insulating Foams – Foam Supplies Inc. • Continued Development of FEA 1100 – a Zero ODP and Low GWP Foam Expansion Agent – DuPont

Environment, Health & Safety 2 Tuesday, 27 September 9, am – 12 pm Dedicated to projects in the spray foam industy, presentations will focus on calculating ventilation requirements, determination of change-out frequency for respirators and an overview of CPI research initiatives in the spray foam sector. Presentations will be made by various members of the CPI committee for Product Stewardship and Regulatory Affairs on SPF. • Predictive Model for PU Blowing Agents Emissions into the House – Honeywell • Ventilation Guidance for SPF Application – EPA, ERG

• CPI Spray PU Foam Insulation – Research Initiative Update • Determination of the Impact of Environmental Variables on the Change Out Frequency for Respirator Cartridges Utilized in SPF Applications – Honeywell

Flexible Foams 1 Tuesday, 27 September, 9 am – 12 pm This year’s conference includes two sessions. The first is dedicated to innovations and new formulations including those containing renewable chemicals.

• New Chemical Technology for the Production of Super High Air Flow Flexible Foams – Bayer MaterialScience LLC • Polyurethane Foam With High Support Factor and Air Flow – Dow Brasil • Low Density HR MDI Based Foams – Dow • Evaluation of New Additives to Maximise the Use Level and Processing Performance of NOPs in Conventional Slabstock Foam – Evonik Goldschmidt GmbH • Biorenewable Aromatic Additives For Flexible Foam Enhancements – CTS and Urethane Consulting Labs

Chemistry & Fundamentals Tuesday, 27 September, 2 – 5 pm Papers presented during this session introduce new building blocks for the urethane industry, with emphasis on bio-based products.

• New Isosorbide Derivatives for Biobased Polyurethanes – Pittsburg States University, Kansas Polymer Research Center • 51B: A New Generation of Additives and Polymer Intermediates – Metabolix Inc. • Synthesis of Biobased Poly(urethane amide) Polymers Without Isocyanate Chemistry – Michigan State University/CHEMS

Construction 2: Advancing the Science of SPF Tuesday, 27 September, 2 – 5 pm This session focuses on the development of low GWP blowing agents and their future

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in CMYK (4C)

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contribution to reducing environmental impact when used in SPF applications.

• A Life Cycle Look at SPF Expansion Agents: Crade to Grave Analysis – DuPont • Honeywell’s Next Generation (LGWP) Blowing Agents for Global SPF Applications – Honeywell • An Investigation of a New Low GWP Blowing Agent for Spray Foam – Arkema • Trends in the Selection of Next Generation Blowing Agents – An International View – Caleb Management Services Ltd.

Elastomers & Footwear Tuesday, 27 September, 2 – 5 pm Focus will be given to the use of new materials with high renewable content, as well as developments in processing equipment in footwear production.

• Dynamic Properties of High-Load Wheels Based on Cerenol Polyol – Anderson Development Co. & Castor Concepts • Further Advances in Footwear Elastomers with Increased Bio-renewable Content – Huntsman International LLC • Multi-Color PU Sole Production by Casting Mini Spots – Desma GmbH • MDI Elastomers Using Di-(2-hydroxyethyl) Disulfide versus 1,4-BDO as a Curative – Anderson Development Co. • Latest Processing Developments for TPU Footwear Production – Desma GmbH

• Polyol Stabilization and Introduction of A New PUR Slabstock Foam Anti-Oxidant – R. T. Vanderbilt Co.

• Rigid PIR Biofoams from Non Food Grade and Renewable Biopolyols – National Research Council Canada & Enerlab

Processing Innovations

Issue sessions

Wednesday, 28 September, 8 – 11 am

Wednesday, 28 September, 8 – 11 am

Technical innovations and advances in several aspects of PU processing will be presented during this session, including low pressure mixing equipment, the handling of liquids and gaseous blowing agents, new foam injection technology for the appliance industry, processing equipment for PU elastomers, and new developments in lab scale machinery.

• Advanced Low Pressure, High Volume Throughput Mixing Equipment – Desma GmbH • New Developments in Gas Loading Units – Hennecke Inc. • Vacuum Assisted Injection Technology for Refrigerator Production, Providing CostEffective Eco Design and Superior Energy Saving – Cannon SpA • New Flexible Machine Concept for Processing All Types of Massive and Cellular Polyurethane Elastomers – Hennecke GmbH • Hi-Temp Urethane Lab Machines – HiTech/FPA

One session will address the important issues of Building Codes. Experts from the PU industry will address recent code changes, standards and certification. In a parallel session, communication professionals will lead an interactive workshop on managing Social Media.

Renewable Content Polyols Wednesday, 28 September, 8 – 11 am

Flexible Foams 2 Tuesday, 27 September, 2 – 5 pm The reduction in emissions from flexible foams is discussed in two papers, followed by the use of methyl formate as a suitable replacement for methylene chloride in foam production. Finally a new antioxidant for the flexible slabstock industry is introduced.

• FR Developments for Low Emissions in Flexible PU Foam – ICL-IP America Inc. • Advance in Reduced Amine Emission Catalyst Systems for Flexible PU Foams – Tosoh Corporation • Ecomate as a Blowing Agent Replacement for Methylene Chloride – Foam Supplies and Purcom Quimica, Ltda., Brazil

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Papers presented during this session will highlight recent advances in the chemistry of renewable polyols derived from soy bean oil, lignin, and corn.

• Polyurethane Rigid Foams From Agrol Polyols – BioBased Technologies • Soy-Based Rigid Foams with Reduced Urethane Loadings – University of Missouri • Lignin Polyol in Production of Oil Based PU Elastomers and Rigid Foams – Synpo & Latvian State Institute of Wood Chemistry • Susterra Propanediol – Evaluating the Structure-Property Relationship in CASE Applications – DuPont Tate & Lyle Bio Products Co. LLC

Table top exhibition A total of 17 companies have so far committed to the table top exhibition, which will run from 11.30 am – 6 pm on 26 September, 9 am – 6 pm on 27 September, and 8 – 11.30 am on 28 September. Exhibitors so far include; Acme-Hardesty, Albemarle Corp., Con-Tek Machine, Cray Valley USA, Emery Oleochemicals, US EPA, ESCO Edge Sweets, Eurotech Distributors, Hennecke GmbH, Hi-Tech Engineering, Honeywell, Huntsman, MCPU Polymer Engineering, Momentive Performance Materials, Polyurethane Process Industries, PU Magazine International, Reaxis Inc., Spray Foam Coalition, and Wanner Engineering/ Hydra Cell. A few tables were still available in mid August.

Closing session A busy final session, commencing at 11.30 am will see the presentation of best paper and poster awards and the industry innovation award. Headlines form the biennial 2010 End-Use Market Survey will be presented by IAL Consultants and economic trend data from the ACC Chief Economist, Kevin Swift. 

www.pu-magazine.com

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

Utech Asia 2011 preview the shanghai New International Expo Centre (sNIEC), located in Pudong, will host the Utech Asia exhibition from 6 – 8 september 2011. the event, organised by Crain Communications in conjunction with China Minmetals 6-8 SEPTEMBER Corporation and the China PU Industry Association, will host more than 150 exhibitors from all categories of the polyurethanes industry, more than 80 of which are Chinese. A series of sponsored sessions will also run in parallel with the exhibition. these will cover rigid foams, flexible foams, footwear and CAsE, and automotive. the exhibition hall will be open on tuesday, 9:30 – 17:00 hrs., Wednesday, 9:30 – 17:00 hrs., and thursday, 9:30 – 16:00 hrs. Visitors can register in advance, online at www.utechasia.nl

Environmental and economic benefits of efficient production machinery to produce rigid and flexible foam are the key challenges facing equipment manufacturers. Saip of Italy has recently opened the most innovative technical centre for the development and production of PU insulation panels called ce|de|pa. During this event Saip will present audiovisual presentations about this centre.

Impianti OMS has metering equipment for every type of PU material as well as process equipment to handle rockwool, PIR and phenolic. The company has a strong position in the suppliy of HP machines to the Chinese boiler and solar heater market. Krauss­ Maffei will exhibit its vast reaction injection processing experience including LFI, spray and skin technologies.

Cutting machinery Albrecht Bäumer (920) AS Enterprises (490) Dexsun Hardware & Band Knife Factory (1117) Elitecore Machinery (1112) Ferken Kirfel (670) Nantong Healthcare (1096) Shaiguan Jiedeli Accurate Machine Co. (1119) Simmons Engineering Corp. (293) Svenic (950)

The following companies will be exhibiting at the indicated stand number.

Machinery & equipment suppliers ABB Engineering (Shanghai) (1130) Annel Chemical Technology (1012) Beamech Group (790) Beijing Donsheng Futian PU Machinery (1125) Beijing Jinghua Park PU Equipment (1068) Cannon SpA (930) Chengdu Dongri Machinery (1099) Dongguan ERS Machinery (1069) Dongguan Foaming Machinery (1082) Dongguan U Long Machinery (1005) Dongguan Zhengfeng Machinery (1003) DUT Korea (605) Elitecore Machinery (1112) Fangyuan Sponge Machinery (1117) German Fluid Systems (910) Hennecke (430)

Impianti OMS (530) King Ray Machines (1019) KraussMaffei Technologies (620) Laader Berg (775) RIM Polymers (850) SAIP Impianti (200) Secmer (520) Shanghai Hemork Chemical (1012) Shanghai Sinhao Equipment (1062) Shanghai Yongming Machinery (1057) Shenzhen Anges Machinery (1015) Sunkist Chemical Machinery (293) Wenzhou Feilong Machinery (1058) Wuhan China Light Machinery (1078) Xianghe County Long Foam Machinery (1128) Xiangtan Jingzheng Equipment (1020) Yang Yu Foaming Machinery (1088) Zhangjiagang Strength & Ind. Machinery (1109) Zheijiang Henhui Machines (1071) Zhongshan Shinnon Machinery (1083)

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New equipment presented will include profile cutting, water jet cutters from Edge Sweets, and storage and conveying equipment from Albrecht Bäumer. Promoting its “Made in Germany” quality, Fecken Kirfel will showcase a new loop cutting line which integrates an automatic bandknife splitter into a loop conveyor to produce rolled goods.

Pumps & dispensing machinery Beijing Gelanex Technology (1025) Graco Inc. (550) Kracht Corporation (700) Kral AG (990) Metal Engineering Co. (390) Oerlikon Barmag (295) OSV Technologia (495) Shanghai Linggang Hydraulic Pump (1031) Shanghai Qiguang Machinery (1007) Toho Machinery (745) Wenzhou Julong Electromechanical (1022) Xingfa Measurement Factory (1036) Zhejiang Lingxin Polyurethane Co. (1035)

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High precision metering of liquids is essential for many polyurethane processes. Barmag will be exhibiting its proven products and services as well as some new developments which allow delivery volumes up to 200 ccm/ rev. Graco Inc. will be introducing new equipment for the Asian spray coating market. The latest screw-type flow meters as well as current products such as flow meters and gear pumps will be displayed by Kracht.

Kracht can also supply pumps for potentially explosive materials. Secmer will introduce its low pressure mixing machines designed for the CASE sector, especially for encapsulation and potting resins. OSV from Ukraine will use the show to launch itself as a new player in the international PU industry.

PU chemicals & additive suppliers Acmos (690) Air Products & Chemicals (650) Albemarle Chemicals (775) Arpadis Polyurethanes NV (480) Asia Polyurethanes (810) BASF (210) Baulé (520) Bayer MaterialScience (270 & 170) Beijing Plaschem Trading (1121) Binhai Chemicals (725) Bomex/ISL (205) Cangzhou Dongsu Group (1111) Chem-Trend (730) Chemtura Shanghai (870) China North Chemicals (1065) Dongguan Hontex Chemical (830) Eastsun Chemicals (1107) Era Polymers (470) Everlight Chemicals (570) Evonik Goldschmidt (630) Foam Supplies (890) Group Jiangsu Zhongshan Chemical (1052) Guangzhou GBS High Tech Ind. (1055) Hairma Chemicals (580) Hangzhou Elion Chemicals (1023) Hebei Yadong Chemical Group (1115) Huntsman Polyurethanes (110) Invista (680) Itoh Oil (460) Jiangsu Harson Imp. & Exp. (1092) Jiangsu Yoke Technology (1122) Jiangyin Yobo Polyurethane (1010) Jinhua Chemicals Inc. (1100) Li Yang Zhen Yu Chemical (1060)

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McLube Asia (710) Milliken Chemical (880) Mitsui Chemicals (780) Momentive Performance Chemicals (150) Mondi (590) Nanguang Chemical Co (1123) Nanjing Dymatic (500) Nanjing Hongbaoli (1037) Nanjing Tinchem Technology (1110) Nippon Polyurethane Industry (610) PCC Rokita (695) Perstorp (970) Productos Concentrol (800) Purplan (600) Qingdao Dehui Fine Chemical (1032) Qingdao Lianmei Chemical (1032) Qingdao XinYutian Chemical (1017) Sanyo Chemical Industry (980) Shandong Bluestar Dongda (1101) Shandong Dongyue Fluoro Silicon (1026) Shanghai Netchem New Mould (1030) Shanghai Ulchem Technology (1076) Shell Chemicals (450) Shepherd Chemical Co. (900) Shijiazhuang Carbonic Materials (1117) Shijiazhuang Hejia Health Products (1105) Sinochem International PU Ltd. (1080) Sinopec/Shanghai Gaoqiao PU (1098) SKC (510) Solvay Fluor (330) Suzhou Xiangyuan Special Fine Chem (1039) Tianjin Zhongxin Chemtech (1095) TMG Chemicals (895) Xiamen Kaiping Chemical Co. (1058) Wuxi Chemicals (760) Wuxi Luoshe Central Chemicals (1036) Yantai Tongxiang Chemical (1033) Yantai Wanhua Polyurethanes (250) Zhejiang Sanmei Chemical (1072) Zhejiang Wansheng Chemical Co. (1079) Zibo Dexin Lianbang Chemical (1067) A complete range of chemicals and additives will be displayed by the leading suppliers, including domestic and overseas manufactured polyols and isocyanates, from BASF, BMS, Bluestar, Huntsman, Jinhua, Perstorp, Shanghai Gaoqiao and Yantai Wanhua. Shell Chemicals will be promoting its new Caradol MD250-10 polyether polyol which enhances the polymerisation and improves the stability and hardness of low density flexible foam. This

product helps producers of these types of flexible slabstock foams in developing markets, where the emphasis is on affordable foams, to also improve the safety of their workers, increase productivity and reduce overall formulation costs. Invista will launch its well known range of aromatic polyols into the Asian rigid foam market during the event.

With more than 30 years of experience in Asia, Evonik continues to offer the most comprehensive range of additives for the PU industry. During Utech Asia the company will introduce new products for the market including catalysts and silicone stabilisers for footwear and microcellular foams and new additives for the new flammability and emission challenges faced by the flexible foam industry. Evonik also supplies foam softening and mould release agents.

Under the slogan “From Megatrends to Business”, Bayer MaterialScience will be showing how its innovation, technology and solutions are helping China, Asia and the rest of the world from rural to urban to meet challenges such as energy shortages, urbanisation, growing population, and climate change.

With its prominent presence at hall W5/ booth 270, Bayer’s booth showcases the cockpit of the inspirational Solar Impulse plane that can fly around the world without

Solar Impulse

using any fuel, innovative technology like polyurethane nanofoam, cold chain solutions to help rural farmers generate more disposable income, and building insulation to reduce energy consumption for buildings in urban areas.

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Bayer will also host two technical seminars during PU China which are open to all visitors: • 6 September 2011 (Tue, 11:00 – 12:00) Rigid Foam Applications in Cold Chain and Construction • 8 September 2011 (Thu, 13:00 – 14:00) EcoTrekker: BMS Solutions for a Greener Footwear Industry Auxiliary products Suppliers of release papers, flexible and rigid PU foams, TPUs, construction materials, adhesives and coatings are also amongst the exhibitors.

Alfa Klebstoffe/Simalfa (860) Austin Novel Materials (820) Dongguan Dongke Paper Co. (1090) FoamPartner/Bock (960) Huzhou Innovative Polyurethane Material (1027) Kanghong Decorative Material (1056) Mondi (590) NCM Hersbit Chemicals (1050) Perfect Chemical Industry (1053) Qingdao Baolong PU Bond & Anticorrosive Co. (1087) Saba Dinxperlo (300) Shandong Lecron Energy Saving Material (1085) Sikerui Polyurethane Co. (1061) Sun Yang Global (1052)

Tecnoelastomeri (230) Tianjin Rubberised Mattresses Co. (1127) Toyo Quality One (1021) Zhejiang Jinggong Science & Technology (1051) Associations & information services Indian Polyurethane Association (H9) Isopa (710) Liming Research Institute of Chemical Industry (1086) Shanghai Beici Business Information (1008) Suntower Business Consulting (1118) Yantai North Chemical Industry Information Co. (1129) 

Better Products with Ecomate

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approved for use in refrigerated appliances and vending machines. It has excellent properties for use in construction applications such as residential doors, building insulation and commercial roofing. Ecomate® also meets the polyurethane needs of automotive and marine industries.

Ecomate is both U.S. EPA and SNAP approved to replace HFCs and SMOG producers such as hydrocarbons. In fact, FSI customers in 2009 alone reduced potential greenhouse gas emissions by 1.2 billion pounds of CO2e, which is 3x more than any competitor.2 So, be kind to the environment and your customers. Make the change to Ecomate. 1

Generally Regarded As Safe (GRAS)

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Our product provides excellent foam insulation for a variety of applications. Ecomate® is GRAS1

Better Products. Better for the Environment.

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Dow and Saip customers inaugurate ce|de|pa

The Dow Chemical Company and Saip Equipment inaugurated on 6 July 2011 with their customers ce|de|pa (“Continuous Panel Development Center”, or in Spanish “Centro de Desarrollo del Panel en Continuo”), a unique in the world initiative conceived to accelerate innovation of polyurethane made panels for thermal insulation used in the construction industry, and produced with continuous double lamination process. ce|de|pa is a 60/40 (Saip/Dow) joint venture located in Tudela (Navarra, Spain) to serve Dow and Saip customers worldwide, and is also open to external R & D and Technology Centers, Universities, Quality Certification organisations, and other external players interested in innovation and sustainability in this industry. The decision for the location was made because of the technology oriented Navarra government that since several years tries to attract new and environmentally friendly industries and subsidises the location. An additional point of course was the proximity to the Spanish Dow systems house in Ribaforada.

“Partnering with Saip in ce|de|pa will surely accelerate the implementation of our Energy Efficiency business strategy in the construction industry that is ultimately based on the differentiation and market success of our customers,” said Herman Motmans, Director for the Energy Efficiency business within Dow Thermosets Systems. “The Dow Energy Efficiency business contributes to Dow’s efforts and results in sustainability. With around 40 – 50 % of all energy in Europe used in buildings, up to 60 % of which used for heating them (PU Europe data, 2009), the construction industry has significant potential to achieve further energy saving in commercial, industrial, and residential buildings. While we help our customers stay ahead and differentiate their own polyurethane systems based offering, we are confident that through ce|de|pa we will be able to translate innovation and sustainability into new profitable business growth, both for our customers and for Dow. ce|de|pa is a new reference for the industry,” Motmans added.

Manager for Dow Thermosets Systems in Europe, Middle East and Africa. “We are investing in new systems and services that meet or anticipate our customers’ demands, and the final markets’ direction and needs. ce|de|pa is an unmatched initiative and the immediate response of our customers has already given us the sense of their appreciation for this industrial scale and state-of-theart development center for Dow and our Energy Efficiency business offering,” Penrice added.

“Perfecting our offering, further improving in our ability to tailor our product range and service level to our customers, and accelerating in our journey towards developing new processing methods and machines: these are the key reasons why Saip has conceived and invested in ce|de|pa with Dow,” explained Luigi Procopio, Commercial Director at Saip. “We are convinced that our customers will highly benefit from the possibility to accessing such a unique center for their

“Dow’s business strategy is to accelerate innovation and foster our customer’s differentiation,” highlighted Jon Penrice, General

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• Flexible facing • Multi stream dosing unit (nine components) • Press conveyor with operating temperature up to 70 °C • Thickness range up to 240 mm • Handling section complete with cooling equipment and packaging • State-of-the-art line process control and supervision system (over 100 parameters constantly monitored and recorded) • Up to 16 cameras monitoring and recording the production/trials

profitable business growth. ce|de|pa is for excellence, and stands alone in the industry; Saip and Dow customers will be first in benefiting from its high value and potential,” Procopio explained.

“Investing in ce|de|pa and partnering with Dow in this initiative represent for Saip, our customers and employees, a further prove that our company keeps growing on solid fundaments, with no hesitation and no compromises, striving to become the long-term supplier of choice for an enlarged customers’ base,” said Walter Pozzi, President of Saip. “In over 30 years of continued business expansion and success, Saip has proven our ability to always anticipate and satisfy our customers’ needs through the tailored development of innovative, full-quality and unique solutions that are recognised and acknowledged by the industry. Our success – including our international cooperation with the United Nations and prestigious Universities – is a proven fact of our employees’ know-how, experience, passion and dedication. This makes our business success possible and generates a level of loyalty in our customers representing for our company the best business card to attract and retain future clients, and talents,” Pozzi said.

polyurethane-made panels for thermal insulation produced with the specific technology of continuous double lamination process. The line includes the whole production process from uncoiling to packing. It has enough space for additional sections (e. g. third layer, connecting systems for coils, dosing units for additional components) and has a high flexibility. The starting point of the 135 m, 210 t line in a 3,800 m2 building is: • Roll forming section for corrugated and flat steel facing profiles with a quick change cassete system • Feeding of various pre-cut insulating materials and facings • Gluing equipment for pre-cut materials • Primer equipment for steel facings treatment (APL)

“As we will always start a new project from this starting point full confidentiality is guaranteed to all customers and experts who are using this industry scale lab”, Francesca Pignagnoli, Global Business Development Leader, Energy Efficiency, Dow Formulated Systems stated. “ce|de|pa has been conceived and realised

by Dow and Saip to accelerate the discovery and availability across the industry of novel solutions able to help increase energy efficiency through enhanced thermal insulation of buildings – while also simplifying and accelerating their construction phase, extending durability and safety including fire performance, and the final users’ comfort,” she added.

More information on ce|de|pa is available at www.cedepa.org. 

ce|de|pa is a state-of-the-art and industrialscale line that will allow Dow and Saip customers, and the construction industry at large, to accelerate the development of novel solutions for the manufacturing of

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Walk the Talk – 2 Generation

he emphasised during a presentation at the recent Europur General Assembly.

nd

Isopa members have been developing the “Walk the Talk” programme since 2006 with the aim of improving safety, health and environmental standards across the global polyurethanes industry.

The voluntary programme focuses on the behavioural safety of everyone involved in the industry and promotes best practices amongst management and workers handling diisocyanates and polyols. It also stimulates the safety dialog and safety improvement.

At the end of 2010, new EU legislation came into effect regarding environmental, health and safety issues for the chemical industry.

REACH regulation and the EU Classification, Labelling and Packaging (CLP) directive were implemented and created a need to refresh and expand the Walk the Talk programme.

REACH aims to implement a high level of protection to human health and the environment. Suppliers and end users along the entire supply chain must therefore demonstrate safe use in order to be in compliance.

“The second generation programme demonstrates our member’s continued commitment to the safe handling and use of these materi-

als,” stated Dr Wolfram Frank, Isopa, General Secretary. “This new version encompasses the important aspects of safety compliance now required under the European REACH programme.”

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Changes in hazard communication

Safety is everyone’s responsibility REACH legislation extends along the whole polyurethane supply chain. Therefore, responsibility for safe handling includes all diisocyanate and polyol users, many of whom are SMEs (small and medium sized enterprises). This information is provided by suppliers in extended safety data sheets (eSDS), many of which contain more than 60 pages of data. Understanding and implementing these documents is the responsibility of plant managers and management, they must ensure that operators also fully understand and can implement the safety requirements.

In the case of SMEs, reaching compliance in this area is time consuming, therefore the Walk the Talk 2nd Generation programme is available online at www.isopa.org. The website also includes material from REACH explaining terms and exposure scenarios to help staff to familiarise themselves with the terms used in eSDS. In addition, ISOPA member companies will use the Walk the Talk material to hold customer workshops to explain how to meet the requirements of safe handling compliance under REACH. Authorities will review safety compliance as part of REACH, making the demonstration of “safe use” essential. The programme covers workplace safety and ventilation, personal hygiene and the use of personal protection equipment, safe material handling, and emergency procedures.

In order to get the message through to downstream users, Ronald van den Bosch, Dow Chemicals, Chair of the Work Group for Walk the Talk has been actively involved in creating and developing the Walk the Talk programme from the beginning. Most recently he has been instrumental in promoting safety to the downstreams users, at customers and through end use associations such as PU Europe and Europur to ensure that their members fully understand their duties. “The entire industry needs to be proactive in stimulating safety dialog at all levels. Safety is everyone’s responsibility,”

The new CLP directive became mandatory for chemical substances on 1 December 2010 and will be mandatory for mixtures on 1 June 2015. The UN GHS (Globally Harmonised System) for classification and labelling has been adopted through the EU CLP directive. The implications are that while the product hazards remain the same, hazard communication has changed. Walk the Talk 2nd Generation provides a useful comparison of symbols, risk phrases and precautionary phrase between the Dangerous Substance Directive (DSD) and the new CLP.

Safety in every language!

To promote the safe handling of diisocyanates and polyols across the entire polyurethane industry the original “Walk the Talk” packages are now available in 24 languages on the Isopa website. Walk the Talk 2nd Generation is currently available in English but will shortly be available in all the main European languages. By the end of 2011, Isopa will also have 2nd Generation updates available for the logistics and miscellaneous chemicals programmes. The Walk the Talk poster has also been updated to include 2nd Generation details.

Isopa at Utech Asia While Isopa remains a European Association it is also involved in global issues such as product stewardship, fire safety, sustainability, and communications. It is the intention of the Isopa Board to share its knowledge with other regional associations, therefore Isopa will be present at the Utech event in Shanghai. During this event, Isopa will be promoting safe material handling through the Walk the Talk programme and the sustainability of polyurethane to the Asian industry. Isopa already cooperates with associations in the USA and Asia through regular global meetings. Representatives from Isopa will be available at stand 710. 

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

Honeywell launches fourth generation high performance, LGWP blowing agent Honeywell will officially launch its latest addition to its “fourth generation platform” of blowing agents for the polyurethane industry during the CPI (Center for the Polyurethanes Industry) Polyurethanes technical Conference, 26 – 28 september 2011, in Nashville, tN, UsA. the first in the series, 1234ze, was commercialised in Europe in the second quarter of 2008.

Honeywell will highlight the improved performance and low environmental impact of its new blowing agent HBA2 or 1233zd(E), in three different applications in papers scheduled to be delivered at the conference.

The first paper, delivered by Jim Bowman, Senior Principal Engineer, will present new data on the use of HBA2 in the appliance sector. He will compare the performance of HBA2 to other blowing agents used for domestic appliances (figs. 1 and 2). The second paper, delivered by Mary Bogdan, Senior Principal Chemist, will provide data from trials of HBA2 in spray foam applied under a range of demanding environmental conditions compared to blowing agents currently in use (fig. 3). The third paper, delivered by Jim Ling, Senior Research Chemist, will highlight the performance of both HBA2 and 1234ze(E) in panel applications.

On a global basis, the industry, individual government regulators, and NGOs continue to seek a low environmental impact and energy efficient solution across all energy consuming applications, including household refrigerators and construction materials.

Honeywell’s latest fourth generation blowing agent demonstrates the company’s intent to

k-factor (BTU in/h ft2 °F)

0,15

Cyclopentane

245fa

achieve these goals through the use of high performance halochemical solutions.

Responding to environmental concerns The use of fluorocarbon blowing agents started in the mid-1950s with trichlorofluoromethane (CFC-11). Concerns over ozone depletion during the 1970s, led to the development of a second generation of high performance blowing agents, the HCFCs, such as HCFC-141b. Although conversion to HCFC-141b reduced the Ozone Depletion Potential (ODP) of the blowing agent by 90 %, subsequent regulation required the phaseout of these blowing agents. A third generation of blowing agents was developed – the HFCs – including HFC-245fa. These HFC materials satisfied the requirements of ODP regulations while retaining the high performance and non-flammability requirements of many insulating foam applications. Honeywell has been the leader in the development of fluorocarbon blowing agents and is now leading the development of a fourth generation fluorocarbon technology, which is driven by the continued need for energy efficient and low environmental impact solutions.

HBA2

0,14 7.1 % 0,13 0,12

9.3 %

11.5 % 15.4 %

0,11 0,10

35 °F

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75 °F

 Fig. 1: k-factor comparison appliance

In its quest to develop these fourth generation materials, Honeywell’s goal was to retain all the positive attributes of the HFCs: high energy efficiency performance, non-flammability, non Volatile Organic Compound (VOC), and ease of conversion. These properties continue to differentiate fluorocarbon blowing agents as the best choice for high performance rigid foam insulation applications and for those applications where a flammable blowing agent is unsafe, too costly to use, or fails to provide the desired foam performance.

As an added benefit, the fourth generation materials were formulated to have a significantly lower global warming potential, reducing the climate change impact of the materials. “We have succeeded in creating a highly energy efficient blowing agent that also has a very low GWP of 7,” said Sanjeev Rastogi, Business Director. “By keeping the good attributes of HFCs, improving efficiency, and dramatically reducing the global warming potential, we are making it even easier for our customers to adopt the new products in both developed and developing countries.”

HBA2: Wonder molecule?

This new high performance material, while containing fluorine, also contains an olefin structure. The presence of a double bond in the molecule backbone makes the haloalkenes a separate and distinct class of materials from their predecessors. The chemical structure results in a much shorter atmospheric lifetime than HFC materials, thereby resulting in a much lower global warming potential (GWP). HBA2 (1233zd) is a liquid blowing agent, making it suitable for use in appliance foams, pour-in-place applications, and spray foam insulation.

“HBA2 is a great molecule that offers improved performance and superior environmental properties compared to today’s blowing agents,” said Dave Williams, Senior Technical Manager. “Results obtained so far have far exceeded expectations. The molecule yields higher energy efficiency than 245fa in all applications we’ve evalu-

217

Blending is a new technology that is developing quickly as end users consider optimisation of cost and performance through the use of various blowing agents. Commercial options for fourth generation blowing agents can also incorporate a combination of the liquid HBA2 and the gaseous 1234ze blowing agents. “This combination has proven very successful for spray foam applied in cold regions, where the properties imparted by the two molecules help to improve the reactivity of the formulation,” explained Bogdan. Blends with other blowing agents, including water, hydrocarbons, and others are under development by Honeywell, and are expected to broaden the choices in blowing agents for customers. For example, in countries where energy standards are high, OEMs can use pure HBA2 as a blowing agent; however, in countries where energy standards are not as high, OEMs can dilute with water to meet the energy performance and also lower costs. Further, as energy standards increase (which they will eventually), they can decrease the amount of the diluent.

“Blends of hydrocarbon with HBA2 could provide a viable option to balance cost with physical properties and thermal insulation requirements for insulated metal panel applications”, said Bowman. “For panel applications that require superior thermal insulation at low temperatures, pure HBA2 or blends of hydrocarbons and HBA2 may provide a better solution than just hydrocarbons.”

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employment of further energy solutions to this refrigerator/freezer platform, such as vacuum insulation panels or compressor modification.”

Benefits of fourth generation molecule HBA2 is a non-flammable liquid by ASTM E-681 test methods, and exhibits no flashpoint or vapour flame limits. In transportation, storage, and in factory use as a blowing agent, HBA2 has no limitations on hazards classification.

Superior appliance performance Energy efficiency standards for refrigerators and freezers continue to increase in most countries. Meeting these energy standards determines whether a refrigerator can be sold in that country. In a recent trial of 22 cubic foot refrigerators and freezers manufactured using HBA2 (to be presented at 2011 CPI conference), the refrigerators exceeded the Energy Star label requirements by an average of 9.5 % (see fig. 2). According to Bowman, “This highly energy efficient household refrigerator/freezer was demonstrated to meet the requirements of ‘proposed’ DOE 2014 energy standard without

• HBA2 is a near drop-in replacement for liquid HFC blowing agents and does not require costly hydrocarbon storage and handling or risk mitigation equipment.

• HBA2 is liquid at room temperature and can be used in most existing foam equipment with little or no modification, minimising or eliminating the need for large capital conversion costs. HBA2 is an extremely promising replacement for foam insulation blowing agents currently in use that can make significant contributions to reducing global warming.

0% Energy consumption relative to US DOE standard (%)

“Regulation and the growing number of ‘green’ builders are the two main issues within the construction industry driving demand for the next generation blowing agents” stated Mary Bogdan. “We are aware of a growing number of architects and specifiers interested in using high performance materials within the passive house concept.

Rigid foams using HBA2 help to meet these requirements.”

At high temperatures polyol premixes made using HBA2 have a 14 % lower vapour pressure than polyol premixes using currently available blowing agents like HFC-245fa, making spray foam formulations easier to handle and to store. “We fully anticipate that, due to the superior properties of HBA2, many end users will start using it ahead of regulatory requirements,” suggests Williams.

Fig. 2: refrigerator energy consumption

-5 % -10 %

HBA2

-15 % -20 % -25 %

9.5 %

-30 % -35 %

0.18

Fig. 3: k-factor comparison spray foam

DOE energy star



k-factor (BTU in/h ft2 °F)

ated, including appliances, spray foam, and panels, while also offering the possibility of lower cost solutions and optimisation of performance through its inclusion in blends.”



245fa

HBA-2 4.2 %

0.16 3.4 % 0.14 2.3 % 0.12

0.10

40 °F

75 °F

110 °F

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The energy efficiency benefits of HBA2, combined with its low environmental impact and safety in use, make it the right choice as a replacement for HFC-245fa, HCFC-141b, and HFC-365mfc for use in foam insulation blowing agents.

Provides both low GWP and low VOC impact Low GWP materials, because of their very short atmospheric lifetime, often prove to be VOC that contribute to ground level ozone formation. The measure that characterises whether a chemical is a VOC is the Maximum Incremental Reactivity (MIR). This measure (MIR) at which chemicals are generally considered to be a VOC, by US regulation, is that of ethane.

The MIR of both 1234ze(E) and HBA2 has been measured at less than the value for ethane, hence both are expected to be classified as VOC-exempt in the US.

The European Union uses a somewhat different measure to characterise propensity for ground level ozone formation – Photochemical Ozone Creation Potential (POCP) – which is reported, and compared to ethane, which has a POCP of 12.3 (Nielsen, University of Copenhagen). 1234ze(E) has a measured POCP of 6.4, well below that of ethane. The POCP of HBA2 is also estimated to be in this range and well below that of ethane.

Global legislative and commercial status Honeywell’s 1234ze(E) has recently been listed as an acceptable substitute for HCFC foams under the US EPA’s Significant New Alternatives Policy (SNAP) programme. In addition, the US EPA Toxic Substances Control Act (TSCA) office has issued a Pre-Manufacturing Notice (PMN) for 1234ze(E), allowing for commercial sale of this product in the US. SNAP listing and TSCA approval for HBA2 has been applied for and is pending.

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In Europe, 1234ze(E) has been registered under REACH and HBA-2 is registered up to 10 t and a higher level of registration is in progress. In addition, 1234ze(E) and HBA2 provide a substantial reduction in greenhouse gas emissions when used in place of high GWP F-gases regulated under the EU F-gas Regulation.

In Japan, both 1234ze(E) and HBA2 have been approved for commercial sale. Product registrations for both 1234ze and HBA2 are ongoing in the rest of the world.

1234ze(E) has been available commercially since 2008, and Honeywell recently announced that it will build a commercial scale plant in Baton Rouge, expected to start up in 2013. HBA2 is expected to be commercially available in late 2012/2013.



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A study in sustainable living SPF lays the foundation for a cutting-edge, sustainable home When Cleantech, a green residential development and consulting company, began conceiving a sustainable showcase home, its top priority was to reduce energy usage in both a sustainable and aesthetically-pleasing fashion. Cleantech built a strong foundation for sustainability by first designing a building enclosure that would stand up to the heating demands in New England.

Cleantech’s showcase home (fig. 1) uses the most sustainable products currently available. It was designed not with disparate sustainable components, but using a systems approach, ensuring that sustainable elements work together. The home features geothermal energy, solar photovoltaic panels, solar thermal hot water, and sustainable materials throughout.

Each of the sustainable products contributes to the home’s current evaluation for a LEED Platinum rating, but the home’s building enclosure laid the foundation for achieving a high level of energy efficiency. “A closed cell spray polyurethane foam (SPF) thermal and air barrier system created an air tight home, minimising heating and cooling cost from air infiltration, which leads to significant energy losses,” said James Farnham, President, Cleantech. Cleantech understood that the 

Fig. 1: Cleantech’s showcase home

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cutting-edge technologies employed to provide energy to the home only made sense once the energy load on the home was minimizsed in an economical fashion. Energy efficiency starts with the building enclosure.

The building enclosure Cleantech recognised that closed cell SPF was the best insulation for creating a tight building envelope, and chose Certain­ Teed’s CertaSpray foam insulation, which is based on technology from Huntsman Polyurethanes. Cleantech chose CertaSpray SPF for its exceptional R-values and reputation for performance, as well as for the structural qualities, moisture vapour retarder and air barrier that closed cell foam provides. Much more than just insulation, SPF offers improved building durability, healthy indoor air quality and enhanced moisture management – all critical factors in building quality homes.

CertaSpray’s closed cell foam insulation was applied in the wall cavities (fig. 2), the underside of the roof deck, on basement walls, and in frame floors over the garage and porch to protect the home against heat, cold, air infiltration, moisture, and sound. 

An additional benefit was the reduced lumber usage that closed cell SPF enabled. Use of SPF allowed the construction company to use 2 x 4 inch framing, while still achieving its targeted high R-value. In addition to reducing lumber usage and costs, 2 x 4 inch framing helped to save on window and door extension jambs and provided additional square footage.

Air tightness and indoor air quality Air tightness was a significant factor in reaching the energy efficiency goals. The home’s air tightness was officially rated to be much better than typical construction (fig. 3). SPF creates an excellent air barrier system, positively impacting energy efficiency, reducing condensation potential, and can improve air quality in the form of reduced allergens, pollutants, and noise.

A blower door test found an air infiltration rate of ~ 0.07 NACH (natural air changes per hour), meaning roughly 7 % of the home’s air volume is replaced hourly via air infiltration. A typical home built in 2002 – 2003 has roughly 55 % of its air volume replaced hourly with unconditioned outside air. Each cubic foot of air that enters via infiltration must be heated/cooled to get the house back to its thermostat set point.

Thus, SPF has a very significant impact on energy efficiency by minimising infiltration of unconditioned air.

Fig. 2: Certaspray’s closed cell foam insulation applied in the wall cavities

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Although the home is tightly constructed, the indoor air quality of the finished home is excellent, with balanced ventilation provided through heat recovery ventilators (HRVs), passing through a filter before entering the home. This allows control of the air exchange with the outside rather than allowing unknown amounts of outside air to enter the home carrying allergens, moisture and noise.

The HRVs recover energy from the exhausted air to provide this controlled air exchange in an energy efficient manner.

Rightsizing heating & cooling systems SPF significantly reduces infiltration of unconditioned air, allowing the heating and cooling design loads of this home to be significantly smaller than normal for HVAC equipment used in the surrounding area.

Achieving LEED’s highest certification LEED assigns points based on energy savings, water efficiency, CO2 emissions reduction, improved indoor environmental quality, and stewardship of resources and sensitivity to their impacts. SPF provided valuable points in several areas for Cleantech’s pursuit of LEED Platinum certification for this home: 

• High quality insulation • Air tightness, typically 0.05 – 0.20 NACH for SPF homes • Design flexibility to easily accommodate ducts in conditioned space

Innovative ideas from our team under one roof.

However, SPF can also contribute in less obvious ways. In the materials and resource category, closed cell SPF can assist in achieving points for material efficient framing. Not only did the high R-value of closed cell SPF allow 2 x 4 inch stud members, the structural properties of the foam increase racking strength and facilitate use of wider structural member spacing. CertaSpray closed cell foam is also Greenguard Children and SchoolsSM certified and meets the testing requirements to get credit for a low emitting material. Lastly, it can also contribute to protection from garage pollutants for credit in the environmental quality category.

Conclusion Cleantech created a truly cutting-edge home in terms of sustainability. In fact, the official building rater suggested that this home will use 60 – 70 % less energy than a home built to existing code standards. The home is currently being used as a teaching centre to showcase sustainable building techniques and design, as well as new products and construction materials used in high-performance homes. 

Fig. 3: Air tightness of typical house compared to sPF house

Visit us at the Fakuma, Friedrichshafen: 18.-22.10.2011 Productronica, Munich: 15.-18.11.2011

Chemicals · Engineering · Services Foam gasketing, gluing and potting with the highest precision. Sonderhoff – THE system supplier for polymer sealing materials, engineering and services.

Typical house 55 % of air is replaced every hour

SPF house 7 % of air is replaced every hour

The best foundation for implementing your ideas. www.sonderhoff.com • info@sonderhoff.com

Source: Air tightness of new US houses: A preliminary report

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

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Insulating prefabricated houses with PU sandwich elements Effective insulation of buildings is becoming increasingly important to conserve energy and minimise CO2 emissions. Whereas many prefabricated houses in Germany continue to be insulated with mineral wool and cork, in UK the construction industry is one step ahead.

Polyurethane sandwich elements have been used to insulate prefabricated houses for about five years now. However, the trend has started conquering Germany.

Scotframe Limited, a Scottish timber frame house company, has opted for polyurethane sandwich elements. The company manufactures its panels with Hennecke technology and then puts them in its houses, considerably reducing costs. Licensee for these specially insulated houses is the British company SupaWall Limited, which provides its know-how for a smooth technology transfer. This also includes an analysis of the building structure and technical calculations for SupaWall license holders.

So that the polyurethane sandwich elements can be made, Hennecke delivers mixing solutions to AutoRIM, Hennecke’s agent for the British Isles. These include HK series metering machines from 650 onwards, metering technology for the blowing agent pentane as well as the hand-held MXL mixhead with deviation and air cleaning system. MXL mixheads are particularly appropriate for areas that are difficult to access and discontinuous manufacture because they are operated by hand.

www.kracht.eu

AutoRIM is a systems integration specialist, manufacturing the presses for discontinuous production of polyurethane sandwich panels, and a year ago it put the line that included the Hennecke wet end into operation at Scotframe in Aberdeenshire.

The advantages of insulating prefabricated houses with polyurethane sandwich elements are obvious: On the one hand, requirements to reduce CO2 emissions (higher insulation demands) as well as rising energy costs (demands for more effective solutions). On the

other, the rising costs in the construction sector (simple and fast installation of polyurethane sandwich panels) and increasingly high transport costs (a growing number of sandwich panel production centres on the ground). Moreover, polyurethane is superior to mineral wool as an insulating material because it coalesces and sticks more completely between facings and the cells are closed, which means that no air can circulate.

Because the cells are closed in polyurethane sandwich elements only a limited amount of moisture can get through. Condensation only forms, if at all, on the outer surfaces. Whereas when mineral wool is used water gets in and the insulation is limited allowing bacteria and fungi to form, says Hennecke. Polyurethane sandwich elements are also better than panels that are filled with mineral wool in terms of fatigue and physical decomposition.

Furthermore, as opposed to in mineral wool in polyurethane there is no movement of air because the insulating gas is bound. 

Production of PU sandwich panels with Hennecke metering technology and discontinuous presses made by AutorIM

Pumps, Flow measurement and Microcontrollers for the Polyurethanes industry

6-8 SEPTEMBER

06. – 08. September 2011 ∙ Please visit us at booth 700 KRACHT GmbH · Gewerbestraße 20 · 58791 Werdohl, Germany fon +49 (0) 2392.935 - 0 · fax +49 (0) 2392.935-209 · mail info@kracht.eu · web www.kracht.eu

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www.LAPOLLA.com

O. Mauerer*

Bayfomox spray foam – a flameretardant polyurethane system with remarkable properties

circuits protected by an enclosure based on Bayfomox continue to function for quite some time.

based on the established polyurethane reactive system bayfomox, which is used to make molded foam items for preventive fire protection, a two-component polyurethane system and a machine configuration have been developed that enable the material to be applied in the form of spray foam coatings. the polyurethane system exhibits exceptional processing, material and fire safety properties. the spray foam coating‘s flame-retardant effect is based on foaming with simultaneous formation of a heat-insulating carbon foam on the surface when the material is exposed to fire or heat.

In addition to its fire safety properties, the coating benefits from good sound insulation properties and an impressive insulating performance. the spray foam contains no halogenated additives, solvents, plasticizers or fibers. Its range of properties is far superior to that of conventional fire protection coatings and flame-retardant insulating foams. besides fire safety properties, this article also looks at the foam’s mechanical properties, the impact of water and chemicals on the coating and the appropriate machine setup for spray application. the molded foam process and spray application are compared using the example of fire protection foam.

1. Bayfomox – the material Bayfomox from Lanxess is a two-component polyurethane raw material system that has become particularly well established in the construction industry. It is used to manufacture molded foam parts for applications in the field of preventive fire protection. When exposed to fire or heat, the parts expand (intumescence) and demonstrate impressive fire endurance. The material’s ratio of polyol to isocyanate can be adjusted as required to create a range of consistencies from flexible and visco-elastic to rigid and stiff. The foam densities of the highly filled system range from approximately 200 kg/m3 for flexible, elastic foams to 800 kg/m3 for rigid parts

with high dimensional stability. Drying agents such as zeolites that bind moisture/water and reduce/prevent foaming need to be used for densities above 350 kg/m3.

Applications for molded parts made of Bayfomox include fire- and flue-gas-proof seals for cable penetrations. The elastic polyurethane molded foam parts adapt to irregularities, can easily be installed without the need for specialist tools and, although plastic, exhibit exceptional fire endurance.

otto.mauerer@lanxess.com Lanxess Deutschland GmbH, business Unit Functional Chemicals, Leverkusen, Germany

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2. Conventional processing of Bayfomox – molded foam process Most polyurethane foam parts with simple geometries – such as “bricks” (see fig. 2), stoppers, profiles, housings, ventilation grilles, backfilled parts, etc. – are manufactured using the discontinuous molded foam process. The polyol and isocyanate components are mixed thoroughly for a short time in an agitator mixer and quickly fed into a sealable mold. Once the mold has been sealed, the reaction mixture can foam to completely fill the cavity. The mixing and filling process must normally take place quickly because the reaction starts in anything from a few seconds to less than a minute. After several minutes, the foam reaction has reached the stage where the polyurethane foam part formed in the mold can be removed. After it has been cleaned and treatFig. 1: 

Carbon foam formation under the effects of fire (intumescence)

Rigid, higher-density grades of Bayfomox are also suitable for stiff, dimensionally stable parts. Even in the event of a fire, the electric 

* Otto Mauerer

Bayfomox has been tested and approved by the Deutsches Institut für Bautechnik (German Institute for Civil Engineering). The material contains no halogens, asbestos, fibers, plasticizers or solvents.

Tab. 1: typical foam formulations with bayfomox

Formulation components

Function

Dosage

bayfomox PA

Polyol

100

bayfomox P

Isocyanate

40 – 60

Hardness from flexible and visco-elastic to rigid

Water

blowing agent

0 – 0.6

Foam density from approximately 350 to 200 kg/m3

Zeolites

Drying

0–2

Foam density from approximately 350 to 800 kg/m3

Myritol

Cell regulator

0.1 – 0.6

Pore size from approximately 0.5 to 4 mm

Catalyst

0–2

reaction speed

(for molded foam only) DMCH (for spray foam only)

Dosage influences

Higher proportion of open cells (if temperature increase insufficient on its own)

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

ed with a release agent, the mold is ready for the next filling process.

– that can be applied to flammable or firesensitive substrates.

Due to long cycle times that cannot be shortened at will, using a discontinuous process of this kind to manufacture molded parts is a time-consuming and labor-intensive undertaking. It is difficult or impossible to use the molded foam process to manufacture parts with thin wall thicknesses, extensive coatings or back-foaming.

When using spray application, there is no lengthy wait for a reaction to finish and no need to remove, clean or condition molds.

Another advantage is that small, mobile spraying machines can be used for in-situ coating of parts and equipment that have already been installed and need to be protected.

4. Bayfomox formulations and grades

3. Spraying – the new application method for Bayfomox Spraying is a more appropriate application method for high coverage speeds, thin coatings or the treatment of complex surface structures. The properties of Bayfomox parts have always appeared attractive for other applications, too. For example, there is potential for the same outstanding fire endurance the material exhibits in a wide range of solid molded foam parts to be achieved with thin coatings – i. e. using much less material

Table 1 lists typical polyurethane foam formulations for making molded parts or for spray application. The dosage is indicated in parts by weight. By slightly varying the percentages by weight of formulation components, the foam’s properties can be adapted to the relevant application.

Bayfomox PA: The system’s polyol component. A highly filled dispersion of solid, fine-particle flame retardants in a highly functional polyol.

 Fig. 2: Cable penetration seal made of elastic, brick-like polyurethane parts

Properties

Method

Unit

Value

Density

DIN 43420

kg/m

210

tensile strength

DIN 53571

kPa

150

Elongation

DIN 53571

%

65

CLD 40 %

DIN 53577

kPa

27

Compression set (50 %)

DIN 53572

%

< 10 32.5

Oxygen index (LOI)

3

IsO 4589

%

smoke density (flaming)

AstM E 662

Dm

96

smoke density (non-flaming)

AstM E 662

Dm

204

Flammability classification

DIN 4102

class

b2

Fire resistance for typical molded parts

DIN 4102

class

F 90

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

Bayfomox P: A polymeric isocyanate (PMDI). This product is adapted for use with the polyol component. The hardness of the molded parts/ coating can be adjusted by varying the amount added. A ratio of 40 parts by weight isocyanate to 100 parts by weight polyol produces a flexible, visco-elastic foam, while a ratio of 60 parts by weight isocyanate to 100 parts by weight polyol results in a rigid, dimensionally stable foam.

Water: Adding water varies the coating’s density.

When combined with isocyanate, water forms carbon dioxide, which causes the coating to foam. If no water is added, the density is approximately 300 to 350 kg/m3 because the raw material already contains a certain amount of water.

Myritol: A triglyceride from Cognis. This cell regulator controls the pore size and proportion of open cells. Adding a small amount opens the cells.

This reduces shrinkage after cooling. Changing the cell structure also modifies the mechanical properties of the polyurethane foam.

Cell regulators are mostly used for molded foams.

DMCH (dimethylcyclohexylamine): A catalyst that accelerates the reaction between the isocyanate and polyol components if reactivity cannot be controlled by temperature alone. High reactivity is required for spray application because the raw materials applied need to harden fast. This helps stop the foam running, a problem that is particularly common when spraying onto vertical surfaces.

Table 2 lists the typical foam properties of a flexible, visco-elastic foam grade with 100 parts by weight polyol, 40 parts by weight isocyanate, 0.4 parts by weight water and 0.1 parts by weight Myritol.

 Tab. 2: typical properties of a flexible foam grade

A formulation of this kind is ideal for making elastic parts or flexible coatings. Flexible foams with this property profile were also used for the tests described below.

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5. Airless spraying – a suitable machine configuration for Bayfomox Spray application of rigid polyurethane foam, for example to insulate buildings, is an established process. A highly reactive two-component polyurethane system is sprayed onto the bare walls. The system normally reacts to create a layer of low-density foam several centimeters thick. Mobile installations are used for on-site application (in-situ foam).

The normally unfilled, low-viscosity and highly reactive polyurethane system is conveyed in heated hoses and used with a 1:1 polyol/ isocyanate ratio.

The challenge for the Bayfomox system was to enable airless spraying for a highly filled, relatively slow system that is used with polyol/isocyanate ratios other than 1:1. In collaboration with FluidSystems GmbH & Co. KG in Haan, Germany, a suitable equipment combination and appropriate processing parameters were defined.

mixing section is cleaned with dried compressed air, which dispenses with the need for solvents. The following machine settings have proved appropriate for a semi-rigid spray foam coating. throughput

3.5 l/min

spray pressure

180 bar

Polyol temperature

85 °C

Isocyanate temperature

60 °C

Polyol : isocyanate ratio

100 : 50

No catalyst was required with the selected temperature profile. No cell regulator was needed either at the low layer thicknesses of < 10 mm. A foam layer approximately 2.5 mm thick was created with each spraying pass.

6. Molded foam process vs. airless spraying Compared with the molded foam processes described above, airless spraying is a particularly attractive option when time is of the essence.

The amount of material used for a spray foam with a density of approximately 250 kg/m3 and a layer thickness of 7 mm is approximately 1.75 kg/m 2. Based on a spray discharge rate of 3.5 l/min and taking into account the relevant densities, the coverage speed is approximately 150 m2/h. The final layer thickness can be achieved with several criss-cross spraying passes in a



Fig. 3/4: Enclosure before (3) and after (4) a fire



Fig. 5/6: Flame-retardant molded foam part during testing (5) and spraying a foam coating onto a thin part (6)

The transportable H-XP2 reactor was used, a standard machine with the following performance characteristics: throughput, maximum

4.8 l/min

spray pressure, maximum

240 bar

Heating capacity, maximum

15.3 kW

Weight

255 kg

Hose length, maximum

94 m

Power supply

400 V, 35 A

The polyurethane system can be processed directly from the containers (e. g. drums) supplied. The polyol component must be stirred thoroughly to re-disperse any material that has settled. The isocyanate component is, as usual, protected against moisture using silica gel filters. Hydraulic feed pumps transport both components from the delivery containers into the hot-spraying unit, where they are dosed and the necessary spray pressure is generated. Instantaneous heaters and heated hoses bring the two components to the required application temperature.

Due to the short reaction time, mixing does not take place until the spray gun stage. The

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single process. The spray foam hardens and is effective in just a few minutes. The fire protection function takes effect immediately after application. The material is applied using the airless method. In other words, it is very finely atomized – not with compressed air but thanks solely to its high material pres

Fig. 7: Flexible bayfomox coating on polyester fabric

sure. This method benefits from low spray losses and low formation of spray mist in the spraying area.

already been installed can subsequently be protected against fires.

Thanks to mobile installations, the process is not confined to a specific location. As a result, components or equipment that have

7. Fire properties



Fig. 8: H-XP2 reactor

Bayfomox foam does not share the fire behavior typical of standard polyurethane foams. Under the effects of fire or heat, the material expands and forms a carbon foam (see fig. 1). This foam insulates the material below, thus protecting it against the further effects of fire or heat. This fire behavior is typical of intumescent coatings and materials that form an insulating layer.

If a Bayfomox foam with the formulation in table 1 is subjected to the standard fire tests for construction materials used in buildings, it achieves the B-2 classification in line with DIN 4102 and the D-s3-d0 classification in line with EN 13823 (SBI test).



Fig. 9 – 11: A bayfomox foam coating before (9), during (10) and after (11) the fire test in line with EN 13823

At first glance, the classifications appear to reflect only average fire behavior. However, the foam’s mechanism of action – i. e. the formation of a homogeneous, stable carbon foam – requires burning or charring to achieve the actual fire protection shown in figure 11.

8. Fire resistance



Fig. 12/13: testing of fire resistance

The protective shield of carbon foam formed by the Bayfomox foam coating offers fire endurance for a period of up to an hour based on DIN 4102-8. Figure 12 shows an insulating element coated with around 7 – 10 mm of polyurethane foam, which was used as a test specimen. Figure 13 shows the specimen after the test, during which it was exposed to an oil burner at a temperature of approximately 1,000 °C for one hour.

A fire endurance classification of F 30 to F 60 can be achieved with a layer thickness of just 7 – 10 mm. As indicated in table 1, the coating can be flexible, semi-rigid or rigid. Naturally, the fire resistance also depends on the substrate and its surface.

Thermal stability, thermal conductivity and

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227

adhesion all play a role here. A coating on flammable wood fiber board 4 mm thick achieves a classification of F 30, while the same coating on a polyurethane insulating foam board coated with mineral non-woven fabric 60 mm thick achieves a classification of F 60. It is therefore always advisable to test the specific material combination.

9. Acoustic properties Polyurethane foam based on Bayfomox has good sound insulation properties. Flexible foam grades provide particularly effective airborne sound insulation. This is because there are several similarities between the flame-retardant material and acoustic foams.

Typical features include the polymer’s high proportion of open cells, high filler content and visco-elastic behavior. The sound insulation was measured as specified in DIN EN ISO 10534-2. The measuring principle is shown in figure 14.

external weathering. Nonetheless, resistance to solvents, operating materials and water is still relevant. For example, it is worth asking whether such foam materials are damaged as a result of water ingress.

Can fire protection properties be lost due to water damage, for instance? To answer this question, a flexible foam with the properties described in table 2 was immersed in water. The foam specimens measuring 194 x 100 x 10 mm were immersed in desalinated water at room temperature for several days. After being removed, dried

and conditioned, the specimens were heated from a distance of 7 cm using a gas camping heater (heat flux density approximately 140 kW/m2). The formation of carbon foam was observed and measured.

If the foam is immersed in water for less than around a month, there is no visible difference in its fire behavior or the formation of carbon foam. Its stability, tested by piercing, is also similar. If this period is exceeded, the intumescence height decreases.

Microphones

Sound, vertical impact

Test tube

Sound, reflected

Specimen Fig. 14: Measurement of sound absorption in line with DIN EN IsO 10534-2

 Measurement of the acoustic pressure at two positions evaluation via Fourier analysis

Sound absorption 1.0

The sound insulation is measured using two different test setups. Different test tubes are used for low and high frequencies and adapted to the relevant frequency. Each specimen therefore produces two absorption curves.

0.9 0.8

Absorption

0.7 0.6 0.5 0.4 0.3

A comparison was made between the sound absorption of a conventional polyurethane insulating foam (density 30 kg/m3) with and without a flexible Bayfomox coating 5 mm thick (see table 2 for properties). The two green curves show a significant increase in sound absorption for the coated insulating foam. Bayfomox demonstrates impressive absorption levels in all frequency ranges.

0.2 0.1 0.0 100 Fig. 15:  sound absorption of insulating foam with and without a bayfomox coating

228

PUR 60 mm, big tube PUR+Bayfomox 60+5 mm, big tube

10,000

PUR 60 mm, small tube PUR+Bayfomox 60+5 mm, small tube

Intumescence height

mm

10. Impact of water and chemicals on the Bayfomox foam Insulating, bonding and fire protection foams that are used in buildings and must satisfy fire safety requirements do not normally need to be resistant to chemicals or

1,000 Frequency (Hz)

Fig. 16:  Intumescence height following immersion in water

20 18 16 14 12 10 8 6 4 2 0

19 16

15,5

17 14

8

0

10

20

30

40

8

50

60

Storage time (days)

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

formulation (index 74) and a slightly overcured formulation (index 110) can be examined.

There is certainly no reason to suspect that materials/installations will be flooded with chemicals, but contact is entirely possible – for example through adhesives, cleaning agents, varnishes or operating materials. The material’s swelling after being immersed in the relevant media for 24 h was therefore investigated. Both a flexible foam as described above and a rigid foam were tested. The rigid foam had a higher dosage of the isocyanate component – 60 rather than 40 parts by weight.

As a result, a stoichiometrically undercured

The swelling was determined as an increase in the volume of specimens measuring 40 x 40 x 10 mm. The swelling was reversible. The specimens returned to their original dimensions once the solvents had evaporated and/or been rinsed out. Only with the flexible, undercured grade did the extraction of non-abreacted polyol components result in slight shrinkage.

Volume change

40

Delta V @ Index 74, %

The insulating performance of construction materials is becoming increasingly important. Such materials should help to save energy. This is particularly important for components that separate living and utility areas from external areas or areas that are not heated. The key here is to minimize heat transfer. Additional insulation based on plastic foams or mineral wool is therefore applied to most construction materials such as concrete or brick.

Although it does not have closed cells, Bayfomox foam benefits from impressively low thermal conductivity. This significantly improves the substrate’s insulating performance.

Delta V @ Index 110, %

30 20 %

11. Thermal conductivity of the Bayfomox foam

10 0 -10

12. Conclusion oil Ol

IR

M

n-

Iso

ive

oil

He

90

2

xa

an op pr

et M

Ac

ne

ol

l ha

on et

at W 100

no

e

er

-20  Fig. 17: Volume change following immersion in solvents

Compared to solid molded foam parts, even relatively thin Bayfomox spray foam coatings can achieve astonishingly long fire endurance. In addition to enabling significantly higher coverage speeds than molded foams, airless spraying in conjunction with appropriate substrates also paves the way for possible new combinations of properties in products. For example, it is possible to significantly improve the fire resistance, insulating performance and sound insulation of a conventional insulating foam.

 Fig. 18: thermal conductivity of construction materials

Such polyurethane foam combinations could, for example, replace the separate installations used to date for insulation, fire protection and sound insulation with a single product.

40

W/mK

10 1.3

1.0

0.76 0.15

0.1

0.065 0.03

m fo a

ox In

su la

tio n

fo m Ba y

W

oo

d

s as Gl

re te nc Co

St

ee l

0.01

The mobile process also makes it easy to subsequently add fire protection to surfaces or installations that are already in place.

 Fig. 19: Coated insulating foams

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

The material remains undamaged even when subjected to repeated short-term wetting and drying, as is typical on building sites during the construction phase, or in the event of water damage. 

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SWD Shanghai completes final phase of Oceanic polyurea coating project

tem as well as the desalinisation operation filtration equipment.

Exceptional challenges for SPUA

spray polyurea elastomers (sPUA) have proven themselves throughout the world as effective anti-corrosion barriers. From applications on bridges and tunnels, and most recently the high speed Chinese railway, spray polyurea elastomers are becoming more and more prevalent in construction projects. A project recently completed by sWD shanghai may represent one of the most extreme, and largest applications of this material.

CITIC Pacific Mining Oceanic Desalinisation Project CITIC Pacific Mining is a wholly-owned subsidiary of Hong Kong listed company CITIC Pacific Limited and is headquartered in Perth. CITIC Pacific Mining is a young company established to manage the company’s first major investment in Australia, the Sino Iron project. The massive Sino Iron project is being developed at Cape Preston, 100 km south west of Karratha in Western Australia’s Pilbara region. It is the largest magnetite mining and processing operation under construction in Australia.

The plant, under construction at Cape Preston in the Pilbara, will use sophisticated filtration technology to supply process water with a final capacity of 140 million l per day, equivalent to the water contained in 56 Olympic sized swimming pools. The desalination unit will avoid using the limited groundwater available in the area. In a world first for this size and type of plant, the majority of construction is occurring in China with giant modules being 

fabricated, assembled and tested prior to shipping. The first module successfully arrived to site in June and at the completion of the project about 60 modules of varying sizes will have made the ocean journey from China.

Located in the Indian Ocean, the project involved the application of SPUA to large caissons and pipelines that are part of a huge desalinisation plant. The project represents a breakthrough for the Chinese SPUA industry. With phase one using more than 150 t of coating material, and phase two using another 80 t, the project is one of the largest single site coating projects undertaken. It was, however, the complexity of the project and the necessary development of new materials that made this project so unique.

The project involved international cooperation with partners in China (SWD Shanghai, PJOE, CITIC), Australia (Engineering Group) and the USA (SWD USA). It included multisteel constructed caissons with volumes over 3,000 m3, the associated pipeline sys-

Fig. 1: Application of sPUA to interior of operation system



• The adhesive strength of steel substrate is required high than 8 MPa. • The cathodic disbondment strength is required to be less than 9.5 mm.

• The spark test voltage needs be 10 kV. The key to meeting these high technical requirements was preparation with a high strength primer and a layer adhesive primer for application (tab. 1 and 2).

The caissons were constructed at a beach base in Northern China, then treated with the SPUA protective coatings. Equipment used included three Graco H-XP3 Reactors and one HV20/35 and Fusion AP Guns (fig. 1).

The timing of the project required that the application had to be made at low ambient temperatures (–5 °C). Whether it was snowing or raining, the application of the SPUA had to maintain excellent quality to meet the

Tab. 1: sWD959D modified PU anti corrosion primer specifications

Property

Test method

Specification

Note

Cathodic disbondment strength @ 65 °C (mm)

sY/t 0315-2005

≤ 9.3

test with main coating sWD900

Adhesive strength (MPa)

HG/t 3831-2006

≥ 8.6

same as above

Corrosion properties

HG/t 3831-2006

same with main coating sWD900

Dense and anti corrosion

Average thickness (μm)

230

The location in the Indian Ocean made the job exceptionally challenging. In addition to general saltwater corrosion and ocean tide impact, the project needed to be built to withstand severe tropical storms and electrical chemical corrosion under the seabed.

The caissons are imbedded into the seabed and emerge from seawater into open air.

Because of this, they endure different physical and chemical attacks. Therefore, the physical and chemical properties for adhesive strength and cathodic disbondment of the SPUA material was strictly specified. The specifications included:

40 – 50

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

demands of the project. Exceptional challenges also came from the complicated internal structure of the operations systems and caissons. For example to vertically up spray on the filtrate board with thousands holes is extremely difficult to avoid the disfigurements.

All of the problems were solved with high quality materials, a spray procedure technical control, and strict coating film quality inspection by cooperation of SWD, PJOE and CITIC.

tank weighed more than 200 t. Due to their size there was no way to avoid mechanical damage in the cutting, welding, loading and shipping process. This created a need for a repair material. Because many of the repairs were in recessed locations and corner points, the new repair material needed to be hand paintable and had to have the same Tab. 3: sWD956G hand brushable (repairing) PUA  coating specifications

The size of the caissons were 3,000 m3 each weighting 350 t. The operation system

Specification

Viscosity @ 25 °C (mPa·s)

160 ± 20

solid (%)

solid (%) Density (kg/m3)

Tab. 2: sWD959C adhesive PU/PUA primer  specifications Property

Property

Note

≥ 55

Specification ≥ 85 0.9 – 0.98

Hardness shore A

95 – 97

shore D

40 – 55

properties as the spray polyurea but with a slow enough reaction time and excellent flow flat characteristics without bubbles or collapsing issues. In response to this need, SWD Shanghai worked with SWD USA to develop a hand paintable elastomer (tab. 3).

The end result was a project that left the engineers very satisfied, and represents a breakthrough success for the Chinese SPUA industry. Due to the success of the project and SWD Shanghai’s strong commitment to product quality and technical management there are now huge opportunities for SPUA applications in the international oceanic marketplace. 

tensile strength (MPa)

17

Elongation (%)

250

Craig Mathews

Impact strength (J)

10

craig.mathews@swdurethane.com

>6

Dry time (h)

8

adjustable

Adhesive strength (MPa)

Operating time (pot life) (h)

1

adjustable

Gel time (min)

5

Average thickness (μm)

50

tack free (min)

10

sWD Urethane Company, Mesa, CA, UsA

dƌƵƐƚĞĚ WĂƌƚŶĞƌƐ Ͳ /ŶŶŽǀĂƟǀĞ ^ŽůƵƟŽŶƐ ^t hƌĞƚŚĂŶĞ ^ŚĂŶŐŚĂŝ Ͳ h͘^͘ dĞů ͗ϬϮϭ ͲϱϭϵϬϱϯϬϭ ǁǁǁ͘ƐǁĚƵƌĞƚŚĂŶĞ͘ĐŽŵ͘ĐŶ ͲŵĂŝů͗ ƐǁĚƉƵΛLJĂŚŽŽ͘ĐŽŵ͘ĐŶ

tŚĞŶ LJŽƵƌ ƉƌŽũĞĐƚƐ ƌĞƋƵŝƌĞ ƉŽůLJƵƌĞƚŚĂŶĞƐ ĂŶĚ ƉŽůLJƵƌĞĂ ĐŽĂƟŶŐƐ zŽƵ ĐĂŶ ƌĞůLJ ŽŶ ^t ^ŚĂŶŐŚĂŝ /ŶƚĞƌŶĂƟŽŶĂů WƌŽũĞĐƚ džƉĞƌŝĞŶĐĞ ͻ DĂŶƵĨĂĐƚƵƌĞ Θ /ŶƐƚĂůů ,ŝŐŚ YƵĂůŝƚLJ DĂƚĞƌŝĂůƐ ͻ EŽ ŚĂůůĞŶŐĞ ŝƐ dŽŽ ŝŐ

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

231

Emery Oleochemicals uses 170 year old legacy to develop renewable ester polyols

– a solution pioneered by Emery Oleochemicals back in 1953, that propelled the company to become the global leader in ozonolysis. Partnering with Emery Oleochemicals, therefore, was a natural choice.

Whilst Battelle did the initial research on the concept of using ozonolysis to make ester polyols, then funded by the Ohio Soybean Council; patents received as a result of this research were subsequently licensed by Emery Oleochemicals. The partnership, which included further funding by Emery Oleochemicals and sampling works with Troy Polymers, saw the launch of three products under the Emerox brand, namely;

Emery Oleochemicals, a name synonymous with the successful development of quality, natural-based chemicals, traces its 170 year history back to 1840. Having gradually established a reputation for innovation, thomas Emery snr’s Cincinnati based ‘Emery Candle Company’, manufactured and produced tallow for oil lamps for about 40 years before the incandescent lamp was invented. It was however, his research in fatty acids around 1842, that marked the brand’s journey to becoming one of the world’s leading oleochemicals companies today.

Poised for further growth with increasing market demands for more environmentally sound, non-toxic, “green” additives; Emery Oleochemicals’ strategic growth plans include expansions in two key areas – Green Polymer Additives and Home & Personal Wellness. Leveraging its global position in green polymer additives with its renowned Loxiol and Edenol brands; its recent breakthrough in the production of renewable ester 

• Emerox 14000 for PU flexible foam • Emerox 14200 for PU rigid foam • Emerox 14100 for polyurethane coatings applications

polyols has grabbed the polymer industry’s attention. In true Emery Oleochemicals fashion, it is not without a story of its own!

Approximately three years ago, Battelle Memorial Institute, a US think-tank “committed to using science and technology as a positive force for change”, developed a novel process for producing ester polyols utilising ozonolysis (to manufacture azelaic and pelargonic acids)

The industry at large has long appreciated the ozonolysis process for its ability to produce polyols that are flexible since it can infinitely vary hydroxyl values, viscosities, and molecular weight. Taking the polyol benefits

Tab. 1: Pilot scale machine evaluation results

Reference Pour date - run - data point IFD (15" x 15" x 4") Density

IFD (25 % original)

Average (PCF)

spread (PCF)

Average (lb-f)

spread (lb-f)

Hysteresis average (%)

support factor average

ball rebound

Airflow crushed 2x (sCFM)

tensile PsI

tear PLI

Elongation (%)

PL04052011-1-1 25 php NOP

1.76

0.05

30.7

2.6

70.1

2.03

36

4.3

11.1

1.18

146

PL04052011-1-2 25 php E14000

1.76

0.03

32.4

3.4

70.6

2.01

36

3.8

11.1

1.14

134

PL04052011-1-3 37.5 php E14000

1.74

0.08

29.1

2.0

70.2

2.05

36

3.3

11.5

1.11

150

PL04052011-1-4 50 php E14000

1.69

0.02

25.9

0.6

69.5

2.00

34

2.9

11.2

0.93

140

PL04082011-1-1 50 php E14000

1.75

0.04

27.9

1.0

68.9

2.09

34

3.1

10.6

0.90

118

PL04082011-1-2 50 php E14000

1.74

0.03

29.4

0.9

67.8

2.08

32

3.0

11.2

0.99

116

Reference Pour date - run - data point 90 %

24 h flex fatigue

Compression set loss (%)

Ht loss (%)

PL04052011-1-1 25 php NOP

3.9

PL04052011-1-2 25 php E14000

3.6

PL04052011-1-3 37.5 php E14000

CAL-117 Vertical non aged

IDL loss (%)

smolder retained (wt.-%)

CharLength average

A_Flame average

A_Glow average

P/F

1.2

20.3

77.6

2.12

none

none

F

1.2

22.9

76.7

1.88

none

none

F

4.4

1.6

24.0

80.9

1.98

none

none

F

PL04052011-1-4 50 php E14000

5.7

1.2

21.4

78.1

2.12

none

none

F

PL04082011-1-1 50 php E14000

5.4

1.5

19.5

79.8

1.96

none

none

F

PL04082011-1-2 50 php E14000

6.1

1.2

21.2

79.2

1.70

none

none

F

232

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

further, the new Emerox series includes ecofriendly additives to compliment those derived from fossil fuel. These new additives promise to be appropriate alternatives relative to petroleum-based products in terms of costs and performance, whilst all being renewable-based!

In one example of a flexible foam application, formulations using various amounts of Emerox 14000 polyol on a pilot scale machine had results very similar to a commercial NOP-based polyol (tab. 1).

Emerox has the ability to infinitely vary the molecular weight, hydroxyl value, and viscosities of its polyols using the ozone process as illustrated in figure 1.

Other advantages of this range versus its fossil fuel-based counterparts include: • Reduced emission of carbon dioxide: For every 1 kg of Emery’s Emerox used, approximately 3.5 kg carbon dioxide is eliminated from the atmosphere.

• Reduced price volatility: Emerox’s base is renewable oils, thus it is not subject to as much future price volatility as petroleum products.

• Better performance: tests show that relative to other renewable polyols, Emery 

Oleochemicals’ Emerox polyols provide improved performance, greater formulation flexibility, and improved value.

Developed in response to growing market needs, the all-around friendliness of these products including of low odour and custommade product performance characteristics for specific applications, allows this range of renewable ester polyols to provide the opportunity for customers to formulate and develop new, more environmentally acceptable products.

With the global PU market currently valued at an impressive 12 million t, Emery Oleochemicals’ growth plans are on track to tap into these vast opportunities. Emery continues to invest in delivering innovative solutions using natural-based chemicals alongside established areas of business and expertise. As the development, marketing and application of sustainable additives grow, it seems certain that more worldwide innovation by end-users in this sector, will follow soon.  Doug Ness doug.ness@emeryoleo.com Account Manager

Fig. 1: some possible variations in Emerox polyol properties using ozonolysis

Polyol average molecular weight

100,000

10,000

Experimental

f = 6.00

Emerox 14100

f = 2.00

f = 10.00

Emerox 14200

f = 4.00

f = 14.00

100 100

200

300

400

Polyol hydroxyl value

www.pu-magazine.com PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

Issue 5/2011 You are exhibitor and would like to see your company’s show highlights included in our Fakuma Special? Simply send us your press release!

Deadline: 1 September 2011

1,000

0

Extensive preview in

Book an advertisement in the October issue and benefit from special distribution at Fakuma and other important global PU related events.

Emery Oleochemicals LLC, Cincinnati, OH, UsA

Emerox 14000

Fakuma 2011 18.10 – 22.10.2011 Friedrichshafen

500

Contact editor Dr. Stephanie Waschbüsch s.waschbuesch@gupta-verlag.de Tel. +49 2102 9345-11 Contact advertising Cynthia Freyer c.freyer@gupta-verlag.de Tel. +49 2102 9345-15 Internet www.pu-magazine.com

233

R. Irnich*

Sustainable production of PU synthetic leather

does not really look like leather. To obtain a suitable, high-quality surface appearance, it is therefore necessary to apply at least another two coats based on solventborne PU raw materials to the coagulate. All in all, the production process involves a large number of heated baths and three drying stages.

sustainability is a multi-faceted concept: It means protecting the environment and conserving natural resources, but it also means operating in a way that ensures a lasting basis for prosperity and a world worth living in. At present, polyurethane (PU) synthetic leather is mainly produced by the coagulation process. However, with the above aims in mind, there is a good alternative, based on the use of solvent-free, high-solids PU dispersions, that makes it possible to produce synthetic leather efficiently, while at the same time saving energy and reducing emissions.

The chemical industry plays a key role when it comes to improving people’s quality of life without using excessive amounts of natural resources. For chemical companies, sustainable development means careful selection of raw materials, ensuring the safe, eco-efficient and environment-friendly manufacture of materials along the entire value-added chain, and developing end products that are durable and harmless in use.

The process commonly used at the moment to manufacture the more than 500 million m2 of PU synthetic leather required each year for such products as furniture, shoes and automotive interiors is not ideal from the sustainability point of view: The raw materials used are generally based on solventborne resins that include toxic dimethyl formamide (DMF). Energy consumption is also very high.

The status quo At present, 98 % of all PU synthetic leathers are produced by the coagulation process.

This involves coating a woven or non-woven fabric with a paste consisting of a poly-

senior Manager business Development Dispersions textile Coatings & specialties“ bayer Materialscience AG, Leverkusen, Germany

234

There is an alternative process, however, that can be carried out on the usual systems and, unlike DMF coagulation, does not require any solvents or toxic substances. This transfer coating process based on highly concentrated PU dispersions therefore meets the demands made on new materials by leading manufacturers of furniture, sporting goods, textiles and automobiles.

urethane polymerized or dissolved in DMF. The fabric is then passed through a succession of water baths with a progressively decreasing DMF concentration. The final bath contains pure water. During this process, a phase transfer with water turns the PU-based paste preparation into a porous, sponge-like layer. Physical precipitation takes places slowly from the outside in, allowing water to penetrate into the coating and displace the DMF solvent. The toxic DMF can be recovered from the process water by distillation.

However, because of the polar character of DMF, there will always be residual amounts in the material, so the process is not entirely compatible with the aim of reducing emissions of volatile organic components (VOC) as much as possible.

In the conventional process, a voluminous, porous coating is obtained as a result of coagulation and heat generation. In the alternative process (fig. 1), a coating with a similar structure is produced by introducing large amounts of air into waterborne PU dispersions to create a foam – just like whipped cream. The density of the foam can be varied from 200 – 800 g/l, depending on the required softness and stability of the end product after drying, by adjusting the amount of air introduced.

After the coagulation process, the fabric has good volume and a pleasant handle, but

The various steps involved in producing synthetic leather are shown in figure 2: First, a

Fig. 1:  scanning electron microscope image of a solventborne PU synthetic leather coating produced by means of coagulation (left) and a mechanically blown foam coating based on new, highsolids PU dispersions (right)

Finish

* Dipl.-Ing. rolf Irnich rolf.irnich@bayer.com

The good alternative

Fig.2:  Production of synthetic leather by means of transfer coating using waterborne PU dispersions

Foam Oven

Oven

Oven

Lamination

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

topcoat is applied on release paper, which is usually embossed with a leather grain. The voluminous layer of mechanically blown foam is then applied via a second die as an intermediate coat. The resultant two-layer coating is laminated with the woven or non-woven fabric, and finally the release paper is removed to give the finished synthetic leather (fig. 3).

Energy requirements halved, emissions ten times lower This alternative process also involves a total of three drying phases between the individual

steps, but these use only around 446 kJ energy per m2 of synthetic leather produced as compared with some 922 kJ for drying in the established process (see tab. 1). In other words, energy consumption is more than halved. The main reason for this is that in the coagulation process, the entire woven or non-woven fabric is saturated with water, which then has to be evaporated.

In trial production runs at Bayer MaterialScience, customers it was found that synthetic leathers produced by transfer coating with waterborne PU dispersions exhibit abrasion and hydrolytic resistances on par with those manufactured by the coagulation proc-

Grained skin coat Foamed intermediate PUD coat PUD-based tie coat  Fig. 3: structure of a synthetic leather based on waterborne PU dispersions

Textile substrate (woven or non-woven)



Tab. 1: Energy consumption of the two alternative production processes for high-quality PU synthetic leather

Process

Coating structure

Energy requirements for drying

based on PU solution

• PEs non-woven 250 g/m2 • Coagulation 150 g/m2 PU dry • transfer coating: two coats with a total of 60 g/m2

• 900 kJ for approximately 400 g/m2 water • 22 kJ for approximately 38 g/m2 DMF Total: 922 kJ

based on PU dispersion

• PEs non-woven 250 g/m2 • transfer coating: 1. Finish with 25 g/m2 PU dry 2. Foam with 150 g/m2 dry 3. Adhesive coat with 60 g/m2 dry



• 86 kJ for 38 g/m2 water • 225 kJ for 100 g/m2 water • 135 kJ for 60 g/m2 water Total: 446 kJ

ess using solventborne PU raw materials (see tab. 2). What’s more, emission analyses in accordance with VDA 278 have shown that the VOC and FOG values are ten times lower.

Dispersions with 60 % solids content The extremely high mechanical and chemical stability of synthetic leathers manufactured by the alternative process is largely attributable to the new polyether- and polycarbonate-based PU dispersions, which in some cases have a solids content of 60 %. This high solids content makes it very easy to produce extremely homogeneous foams with a wide range of densities (200 – 800 g/l). It is also possible to apply sufficiently thick, compact coats in one operation. And finally, high-solids dispersions cut storage and transport costs.

A solids content of 60 % is not easy to achieve. After all, even the most tightly packed spheres in a crystal occupy only 74 % of the available space. And if spheres of equal size are thrown loosely onto a pile, the resultant density is a mere 64 % – the experimental upper limit for free-flowing materials. So the latest generation of PU dispersions comes very close to this physical limit. The research scientists at Bayer MaterialScience achieved this by means of skillful bimodal distribution of the particles in the dispersion or, to put it more simply: The dispersion contains small

Fig.4: the bimodal particle size distribution of the latest generation of PU dispersions permits a very high solids content of 60 % Bimodal particle size distribution

A higher density is possible

10

100 ΣCi Co

8

6

80

60 [%]

[%]

Particle size [in 10-6m]

4

40

2

20

0

0 0.0

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

0.2

0.4

0.6

0.8

1.0

235

spheres that fit into the gaps between the larger spheres (fig. 4).

An example for the “60 % generation” is Impranil DLU, an aliphatic PU dispersion featuring good foaming characteristics, elasticity, and hydrolytic resistance. As they are free of organic cosolvents and external emulsifiers, these high-solids dispersions (see tab. 3) can also be used as a compact intermediate coat in a four-layer structure to produce particularly high-quality synthetic leathers for furniture or automotive interiors, for instance.

Such synthetic leathers have exceptionally good scuff and abrasion resistance and good resistance to cracking.

Potential for even greater sustainability Of course, sustainability means more than just cutting energy consumption and emissions and manufacturing goods as efficiently as possible. Another important aspect is reducing our dependence on fossil resources.

Two of the many possible ways of achieving this are using renewable raw materials and recovering raw materials from the polymers.

Bayer is already looking for ways of using 

the renewable raw materials offered on the market and is also involved in research projects. Bayer Technology Services, for example, is a partner in a lignocellulosic biorefinery research consortium. This project has now reached the second phase, during which a pilot plant will be constructed and commissioned at the chemical/biotechnological process center in the Leuna chemical park. All the main components of beech and poplar wood – cellulose, hemicellulose and lignin – are to be used equally to produce important platform chemicals.

The starting materials for polyurethanes are isocyanates and polyols. While research into the manufacture of aliphatic components from renewable resources is already at an advanced stage, investigations into the production and recovery of isocyanates and aro-

matic raw materials are still in their infancy.

As regards polyols and aliphatic raw materials, Bayer MaterialScience has already developed a PU dispersion using a polyol based on a renewable resource. The property profile of this dispersion is comparable in all respects to that of Impranil DLS. The range of products available is expected to expand in the near future. For the time being, however, bio-based polymers only stand a chance on the market if they are at least as good as polymers based on fossil resources. Furthermore, the renewable raw materials should not come from plants or plant components that are needed for food production. The processes and reactors developed by H&S Anlagentechnik of Sulingen, Germany, for example, show that it is possible to recover polyols chemically by depolymerizing polyurethanes. 

Adhesion (in kg/cm) Dry: Wet: Total VOC mg/kg Abrasion resistance Tab. 2:  (taber test 1000 cls/stone H22, 10N) Comparison between the Hydrolysis resistance properties of solventborne tropical test: 70 °C; and waterborne synthetic 95 % relative humidity leathers

Solventborne

Waterborne

4,0 3,8

> 5,0 > 5,0

> 500

< 50

28 mg

23 mg

< 4 weeks

6 weeks

Tab. 3: Properties of PU dispersions with a solids content of 60 % Impranil DLU Polyether/ Polycarbonate-Polyurethane

Impranil LP RSC 1537 Polyester-Polyurethane

Impranil LP RSC 1554 Polyester-Polyurethane

Impranil LP RSC 1380 Polyester-Polyurethane

100 % Modulus [MPa]

2–3

tensile strength [MPa]

20 – 30

1.2

3

1.0

13

26

Elongation at break [%]

14

600 – 800

1,200

1,300

1,300

500

120

300

400

swelling in water [%]

13

10

7

10

Hydrolysis

++

+

0

0

Melting point [°C]

200 – 300

200 – 210

210

215

shore A hardness

60

55

65

55

Light fastness

7

7

7

7

Physical properties

swelling in ethyl acetate [%]

236

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

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under the permission of TOBB according to the law 5174

237

J. Kang, G. Erdodi, J. P. Kennedy*

A new class of TPEs: Melt processible polyureas

use of chain extenders (CEs) or by drastically reducing the hard segment content (to 5 – 14 %). Sherman et al. prepared melt processible polyureas with ~1 % hard segment by reacting polyisocyanates and polyamines [7]. Decreasing the hard segment content, however, compromises mechanical properties. Recently Rinaldi et al. [8] prepared melt processible polyureas with 15 – 25 % hard segments by the use of branched CEs; however, branched CEs also strongly reduce mechanical properties [9].

Polyureas, due to the presence of strong bidentate H-bonds in the hard segments, do not melt (they degrade before melting) and therefore must be processed in solution (e. g., by dry spinning) by the use of costly and environmentally unfriendly solvents. We set out to render polyureas melt processible, i. e., to reduce their flow temperature, tflow, while maintaining their outstanding mechanical properties. We hypothesized that melt processible polyureas could be obtained by reducing their tflow way below 200 °C using combinations of conventional chain extenders (CEs) and small amounts of H-accepting chain extenders (HACEs). Conventional CEs merely lengthen the hard segments, whereas HACEs are dual-purpose CEs that lengthen and flexibilize the hard segments. We document the synthesis of conventional polytetramethylene oxide (PtMO)-based and novel polyisobutylene (PIb)-based polyureas with tflows ~180 °C and excellent mechanicals upon the addition of few percents of commercially available HACEs. Products were characterized by various techniques, including Instron, durometry, DMtA, and tGA. A micromorphology for HACEcontaining melt processible polyureas is proposed.

1. Introduction TPE polyurethanes and polyureas comprise soft/rubbery polymer segments linked to incompatible hard/crystalline segments that provide physical crosslinks and reinforcement [1]. Polyureas typically exhibit superior mechanical properties to polyurethanes due to the presence of strong bidentate H-bonds between urea (-NHCONH-) groups [1, 2]. Figure 1 shows the different types of H-bonds that exist in the hard segments of polyureas and polyurethanes.

The ultimate properties of polyureas and polyurethanes are mainly due to the nature, composition, and morphology of the soft and hard segments [1]. Further, the nature and extent of H-bonds within the hard segments and between the hard and soft segments, strongly

affect mechanical properties and processibility [1]. Polyureas degrade upon heating to 240 – 250 °C before they start to flow [3]. A well known example is Spandex Lycra polyurea fiber, processible only by solution techniques (dry spinning) by the use of strongly H-accepting solvents (e. g., dimethyl formamide) [4, 5]. Due to the use of such solvents the processibility of polyureas is costly, cumbersome, and environmentally unfriendly.

We set out to synthesize melt processible TPE polyurethanes and polyureas with at least ~30 % hard segment, exhibiting heretofore unattainable combinations of desirable physical-chemical-biological-processing properties [10]. We theorized that our objective could be achieved by the use of combinations of conventional CEs with small amounts of H-bond accepting CEs (HACEs) [10]. In contrast to conventional CEs (e. g., 1,4-butane diol) that lengthen/stiffen the hard segments, HACEs are dual-purpose CEs that lengthen and flexibilize the hard segments; flexibilization is due to the inherently mobile HACE segments (typically oligoethers) of Mn = 150 – 650 g/mol (representing 3– 15 O atoms) that produce H-bridges within the hard segments. The HACE concept, a new paradigm in polyurethane technology, was introduced and discussed in [10].

A thorough examination of the scientific and patent literature revealed a variety of methods developed to render polyureas melt processible; however, all these methods call for major changes in their synthesis. For example, Sheth et al. [5] and Das et al. [6] achieved melt processibility by avoiding the

By the use of HACEs we recently prepared polyisobutylene (PIB)-based polyurethanes with outstanding mechanical properties and unparalleled oxidative-hydrolytic resistance, e. g., ~30 MPa tensile strength, ~700 % elongation, ~75 Shore A hardness, and ~100 % retention of mechanical properties

H H

H

N

N

O

N O O

* Jungmee Kang, Gabor Erdodi, Joseph P. Kennedy josep19@uakron.edu Department of Polymer science, University of Akron, OH, UsA

238

Fig. 1:  structures of H-bonds in the hard segments of polyureas and polyurethanes

H

H

H

N

N

N

O

O

O

Bidentate (bifurcated) H-bonds in polyureas

H-bonds in polyurethanes

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

after prolonged exposure to aggressive chemicals, such as 35 % nitric acid [10, 11].

Specifically, we hypothesized that melt processible polyureas could be prepared by the use of conventional CEs in combination with small amounts of inexpensive commercially available HACEs. We expected that CE+HACE combinations would produce H-bonding of sufficient strength for good mechanical properties together with increased hard segment mobility for melt processing.

Figure 2 shows the structure of HACEs used in this research.

This paper concerns the synthesis, characterization, and testing of melt processible conventional PTMO-based and novel PIBbased polyureas prepared by the use of CEs+HACEs combinations. All these polyureas exhibited excellent mechanical properFig. 2: structure of HACEs used



O HO

(CH2)4O BG9

H HO [(CH2)5 or 6OCO]2 or 3 (CH2)5 or 6OH 9

HO-PC-OH

2.2 Syntheses

ties and low flow temperatures (i. e., Tflow <200 °C) suitable for thermal processing.

2.2.1 Synthesis of PTMO-based HACEcontaining polyurea-urethanes

2. Experimental

Polyureas and polyurea-urethanes were prepared with amine-telechelic polyols plus combinations of CEs and HACEs by the two step prepolymer method. Thus prepolymers were synthesized by reacting H2N-PTMO-NH2 and HMDI in THF solution at room temperature for 5 min. Subsequently HDA and HO-PC-OH were added drop wise, DBTDL catalyst was added, and the system was stirred at 60 °C for 3 h to complete the reaction. Films were cast, dried, and stored for a week at 4 °C to accelerate the formation of hydrogen bonds in the hard segment. Samples were stored at room temperature in a vacuum oven until characterization (a detailed synthesis is given in [13]).

2.1 Materials Amine-telechelic poly(tetramethylene oxide) (H2N-PTMO-NH2) of Mn = 1,100 g/mol, hydroxyl-telechelic PTMO of Mn = 650 (BG9), poly(ethylene glycol) of Mn = 400 (EG 9), 1,6-hexamethylene diamine (HDA), and dibutyltin dilaurate (DBTDL) were purchased from Aldrich and used without further purification.

Bis(4-isocyanatocyclohexyl)methane (HMDI) was purchased from Aldrich and used after vacuum distillation. Reagent grade tetrahydrofuran (THF) was purchased form Fisher Chemicals and was freshly distilled. Hydroxyl-telechelic poly(pentamethylene-co-hexamethylene carbonate), 50 mol % each, of Mn = 800 and 500 g/mol (HO-PC-OHs), were provided by Chori America, Inc., Jersey City, NJ.

2.2.2 Synthesis of a PIB-based HACEcontaining polyurea-urethane

Amine telechelic PIB (H 2 N-PIB-NH 2 ) of Mn = 3,500 g/mol was prepared by a wellestablished method [12].

The prepolymer was obtained by reacting H2N-PIB-NH2 and HMDI in THF at room temperature for 30 min. Subsequently HDA and

Tab. 1: Mechanical properties and flow temperatures of PtMO-based conventional (no HACE) polyureas compared with those of HACE containing polyurea-urethanes.



Sample

Composition

Urethane/urea (mol %/mol %)

Tensile strength (MPa)

Elongation (%)

Tflow (oC)

Conventional (no HACE) PtMO-based polyureas C-1

H2N-PtMO-NH2 (1.1 K, 75 %)/HMDI+HDA = 25 %

0/100

31.1 ± 0.1

1,000 ± 7

171

C-2

H2N-PtMO-NH2 (1.1 K, 70 %)/HMDI+HDA = 30 %

0/100

51.4 ± 1.6

849 ± 26

183 ± 2

C-3

H2N-PtMO-NH2 (1.1 K, 65 %)/HMDI+HDA = 35 %

0/100

58.2 ± 0.6

744 ± 4

230 ± 2

7/93

55.5 ± 0.1

820 ± 11

193

PtMO-based HACE-containing polyurea-urethanes PtMO-1

H2N-PtMO-NH2 (1.1 K, 65 %)/HMDI+HDA+HO-PC-OH (0.5 K, 3.2 %) = 35 %

PtMO-2

H2N-PtMO-NH2 (1.1 K, 65 %)/HMDI+HDA+HO-PC-OH (0.5 K, 3.8 %) = 35 %

8/92

56.2 ± 1.3

770 ± 55

203

PtMO-3

H2N-PtMO-NH2 (1.1 K, 65 %)/HMDI+HDA+HO-PC-OH (0.5 K, 4.5 %) = 35 %

10/90

58.4 ± 2.4

910 ± 36

180 ± 8

PtMO-4

H2N-PtMO-NH2 (1.1 K, 65 %)/HMDI+HDA+HO-PC-OH (0.5 K, 5.7 %) = 35 %

12/88

46.5 ± 3.8

910 ± 29

172 ± 2

PtMO-5

H2N-PtMO-NH2 (1.1 K, 65 %)/HMDI+HDA+HO-PC-OH (0.8 K, 6.3 %) = 35 %

9/91

56.2 ± 0.4

866 ± 6

177 ± 1



Tab. 2: Mechanical properties of PIb-based HACE-containing polyurea-urethanes.

Sample

Composition

Urethane/urea (mol %/mol %)

Tensile strength (MPa)

Elongation (%)

PIb-1

NH2-PIb-NH2 (3.5 K, 70 %)/HMDI+HDA+bG9 (0.65 K, 7.5 %) = 30 %

17/83

13.2 ± 1.9

263 ± 30

PIb-2

NH2-PIb-NH2 (3.5 K, 70 %)/HMDI+HDA+bG9 (0.65 K, 9.1 %) = 30 %

23/77

23.3 ± 0.7

434 ± 11

PIb-3

NH2-PIb-NH2 (3.5 K, 70 %)/HMDI+HDA+bG9 (0.65 K, 11.8 %) = 30 %

32/68

22.4 ± 0.3

557 ± 9

PIb-4a

NH2-PIb-NH2 (3.5 K, 70 %)/HMDI+HDA+bG9 (0.65 K, 14.0 %) = 30 %

41/59

24.1 ± 0.6

671 ± 9

PIb-5

NH2-PIb-NH2 (3.5 K, 70 %)/HMDI+HDA+bG9 (0.65 K, 14.4 %) = 30 %

43/57

23.3 ± 0.1

615 ± 7

PIb-6

NH2-PIb-NH2 (3.5 K, 70 %)/HMDI+bG9 (0.65 K, 16.1 %) = 30 %

55/45

22.4 ± 1.1

862 ± 42

a

tflow and hardness of PIb-4 are 178 °C and 73 shore A, respectively.

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3.1 Thermally processible PTMObased polyurea-urethanes

BG9 were added drop wise, DBTDL catalyst was added, and the system was stirred at 60 °C for 3 h to complete the synthesis.

Films were cast, dried, and the samples were stored for a week at 4 °C to accelerate the formation of hydrogen bonds in the hard segment. Samples were stored at room temperature in a vacuum oven until characterization (a detailed synthesis is given in [13]).

Table 1 summarizes compositions, mechanical properties and flow temperatures of representative PTMO-based polyurea-urethanes. Samples C-1 through C-3 show data obtained with conventional (no HACE) PTMObased polyureas containing 25, 30 and 35 % hard segments. As anticipated, increasing the hard segment content from 25 – 35 % increased the tensile strengths from 31.1 to 58.2 MPa, decreased elongations from 1,000 – 740 %, and increased flow temperatures from 171 – 230 °C. A Tflow of 230 °C may be too high for thermal processing due to possible degradation [3].

2.3 Characterization Melt processibility was assessed in terms of flow temperature (Tflow) determined by dynamic mechanical thermal analysis (DMTA).

Figure 3 shows a representative DMTA trace indicating Tflow of sample C-3 in table 1. Stress-strain data were obtained by Instron and degradation temperature by thermal gravimetric analysis (TGA). Characterization details are given in [13].

In view of the excellent mechanical properties exhibited by sample C-3 we selected this product for experimentation aimed at reducing Tflow. Samples PTMO-1 through PTMO-5 show the effect of the addition of a HACE, a commercially available polycarbonate diol (HO-PCOH), relative to that of sample C-3. In view of the strong H-bond accepting character of the carbonate (-O-CO-O-) group, we expected that even a small amount of this HACE will suffice to disrupt the H-bridges between urea groups and thus bring about thermal processibility.

Indeed, by increasing the amount of HO-PC-OH from 3.2 – 6.3 % (see PTMO-1 to PTMO-5) Tflow decreased significantly relative to that of C-3, while the tensile strengths remained essentially unchanged. Importantly, T flow,PTMO-5 dropped some 53 °C (to 177 °C) relative to

3. Results and discussion Our hypothesis that melt processible polyureas can be obtained by combinations of CEs+HACEs (see introduction) was substantiated by two series of experiments: In the first series we prepared conventional PTMObased polyureas and studied the effect of the addition of a HACE (HO-PC-OH) on mechanical properties and Tflow. In the second series, similarly, we prepared PIB-based polyureas and investigated the effect of a HACE (BG9) on these parameters.



A representative DMtA trace (consisting of E’, E’’, and tan δ traces) of a PtMO-based polyurea (sample C-3 in table 1); Arrows indicate tflow at ~230 oC. 1.E+09

1.E+07

E'

0.6 0.4

In view of their compositions, the products shown in table 2 (30 % hard segment plus 7 – 16 % HACEs) should be melt processible, i. e., should exhibit Tflow <200 °C. To confirm this expectation, we determined the Tflow of

50

no HACE

40

0.2

tan δ

-20

80 Temperature (°C)

240

Table 2 summarizes compositions, urethane/ urea ratios, and mechanical properties of PIBbased polyurea-urethanes prepared with a commercially available polyether-based HACE, BG9 (samples PIB-1 through PIB-6). According to previous studies, BG9 improves the mechanical properties of PIB-based polyurethanes [10] therefore, this HACE was selected for the current study. We decided not to use HO-PC-OH in conjunction with PIBbased polyurethanes or polyureas because this HACE, while giving similar tensile strengths, reduced elongations by ~50 % below that obtained with BG9 [14].

with HACE

0.8

E''

1.E+04 -120

3.2 Thermally processible PIB-based polyurea-urethanes

60

1.E+06

1.E+05



Figure 4 depicts tensile strength vs. Tflow of PTMO-based polyureas relative to polyureaurethanes. The Tflows of products synthesized with HACE are significantly lower than those of conventional (no HACE) polyureas, while tensile strengths remain unchanged. According to the Tflows, these polyurea-urethanes are expected to be thermally processible below ~200 °C.

tensile strength vs. tflow of conventional (no HACE) PtMO-based polyureas (, controls) and HACE-containing polyurea-urethanes (). Note the significant left shift toward lower tflows of the HACE-containing products.

1.0

tan δ

E' or E'' (Pa)

1.E+08

Fig. 4:

Tensile strength (MPa)

Fig. 3:

that of Tflow,C-3= 230 °C, while the mechanicals remained essentially unchanged (tensile strengths 58.2 and 56.2 MPa).

180

0.0 280

30 160

180

200

220

240

Tflow (°C)

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the nature of the terminal groups (HO- or NH2-), the CEs (HDO or HDA), and the amount of HACE (5.2 or 14 % BG9). Sample 1 contains only urethane linkages. By changing to urea linkages, i. e., by replacing HO-PIB-OH with NH 2-PIB-NH 2 (sample 2), the tensile strength increases from 17.4 to 19.0 MPa and elongation decreases from 480 to 310 %. The addition of a few percent of HACE (5.2 % BG9) significantly increases both tensile strength and elongation to 24.2MPa and 570 %, respectively (sample 3). Tensile strengths remain the same when HDO is replaced with HDA (sample 4). Significantly, the amount of a HACE that produces the similar tensile strengths is very different: While sample 3 contains only 5.2 % BG9, sample 4 contains 14.0 %. This indicates that a larger amount of HACE is needed to flexibilize, i. e., loosen, the hard segment in the polyurea than in the polyureaurethane.

a representative sample (PIB-4) and, indeed, found T flow= 178 °C (see footnote to table 2). The hard segment content of 30 % was selected because polyurethanes with 30/70 hard segment/PIB exhibit unparalleled oxidative/hydrolytic stability [15].

Therefore, the focus of this research was to document the improvement of mechanical properties by the addition of HACE. The effect of HACE concentration on mechanical properties is shown in figure 5: Tensile strengths and elongations increase with the concentration of the HACE. In the absence of the conventional CE (HDA) tensile strength decreased somewhat (see the last data point in the figure). To obtain optimum mechanical properties the H-donating and H-accepting groups should be balanced, i. e., the number of -NH- (donating) groups must balance the number of H-accepting sites (e. g., -O-, -O-CO-O-) which include those in the HACEs.

3.3 Thermal stability The data in table 3 serve to compare the mechanical properties of a representative PIB-based polyurethane and three polyureas containing 30 % hard segments by varying

The thermal stability of a representative polyurea-urethane was investigated by TGA. Figure 6 shows the TGA trace of PIB-4 in air

Tab. 3: Comparison of mechanical properties of a PIb-based polyurethane and three polyureas prepared  with various chain extenders and amounts of HACE. Tensile strength Elongation (MPa) (%)

Sample

Comparison

1a

HO-PIb-OH (3.5 K, 70 %)/HMDI+HDO = 30 %

17.4

480

2a

NH2-PIb-NH2 (3.5 K, 70 %)/HMDI+HDO = 30 %

19.0

310

3a

NH2-PIb-NH2 (3.5 K, 70 %)/HMDI+HDO+bG9 (0.65 K, 5.2 %) = 30 %

24.2

570

PIb-4

NH2-PIb-NH2 (3.5 K, 70 %)/HMDI+HDA+bG9 (0.65 K, 14.0 %) = 30 %

24.1

671

a

Effect of bG9 concentration on mechanical properties. (,  = presence of conventional chain extender; ,  = absence of conventional chain extender).



400

10 200

5 0

5

8

11 14 BG9 (wt.-%)

17

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20

0

Retention of weight (%)

15

Elongation (%)

Tensile strength (MPa)

600

1 % weight loss: 234 °C

100

800

20

Figure 7 shows idealized micromorphologies of polyureas in the absence and presence of HACE. The conventional polyurea (sketch on the left) contains many strong bidentate H-bonds between the urea units and consequently its Tflow is high, which obviates thermal processibility. In contrast, H-bonding in polyureas prepared with polycarbonate- or polyether-based HACE is looser (sketch on the right), which lowers the Tflow and leads to thermal processibility. In the presence of HACEs, H-bridges form not only between urea groups but also between urea groups and HACEs, i. e., the HACEs and urea groups compete for H-bonding. The H-bonds due to HACEs flexibilize the hard segments, improve mechanical properties, and reduce Tflow (i. e., impart thermal processibility).

Fig. 6: the tGA trace of sample PIb-4 in air.

30 25

3.4 Morphology

The purpose of using HACEs is fundamentally different in PTMO- and PIB-based polyureas: whereas in PTMO-based polyureas HACEs loosen the H-bonding between urea units and thus decrease Tflow, in PIB-based

reported in [10]

Fig. 5: 

indicating ~1 and ~5 % weight loss at ~234 and 273 °C, respectively. The trace indicates a two step degradation pattern: The first step at ~270 °C denotes the degradation of urea and/or urethane linkages, while the second step at ~350 °C indicates the degradation of the soft PIB segment [16, 17]. Because the Tflow of PIB-4 is 178 °C, this polyurea is expected to be thermally processible in the 178 – 234 °C range without degradation.

5 % weight loss: 273 °C

80 60 40 20 0 0

50

100

150

200

250

300

350

400

450

500

Temperature (°C)

241

polyureas HACEs flexibilize the hard segments and thus lead to improved mechanical properties [10].

The molecular weights of HACEs must be carefully chosen. It was shown that the mechanical properties of PIB-based polyurethanes are optimum when the molecular weight of HACE is in the 150 – 650 g/mol range [10]. Although the repeat units of PTMO and BG9 are identical we found PTMO with Mn=1,000 g/mol inefficient as HACE; However, BG9 of Mn = 650 g/mol improved mechanical properties.

Similarly, the conventional CE 1,4-butane diol (Mn = 90 g/mol) is an inefficient HACE, although its structure is very similar to that of BG9. Evidently, at the same hard segment content, a low molecular weight diol leads to a larger number of urethane linkages than a higher molecular weight diol. An increased number of urethane linkages increases the extent of H-bonding, which in turn stiffens the hard segments, yields undesirably high phase separation, and thus poor mechanical properties.

4. Conclusions Polyureas cannot be melt processed because of the presence of strong bidentate H-bonds in the hard segments. Typically, these materials are processed by dry spinning, a process which is relatively costly and uses environmentally unfriendly solvents. In the course of these investigations we generated increased insight into the microstructure of polyureas that lead to a simple technique to render polyureas melt processible.

Specifically, we discovered that by the use of just a few percents of HACEs the strength of H-bonding in polyureas can be reduced, which in turn significantly enhanced their ability to flow (i. e., reduced their flow temperatures). In this manner we were able to obtain polyureas with excellent mechanical properties and Tflows of ~180 oC, which allows convenient melt processing. The beneficial effect of HACEs was demonstrated with PTMOand PIB-based polyureas, both containing ≥ 30 % hard segments.

242

5. Acknowledgements We thank Chori America, Inc. for providing the hydroxyl-telechelic polycarbonate.

6. References [1] Gall, H.; Wolf, K.-H. In Polyurethane Handbook; Oertel, G. Eds.; Hanser, New York, 1985; 577 – 591.

[2] Abouzahr, S.; Wilkes, G. L.; Ophir, Z. Polymer 1982, 23, 1077 – 1086.

[3] Li, X.-L.; Chen, D.-J. J Appl Polym Sci 2008, 109, 897 – 902.

[4] Walter, S. (Dupont) U.S. Patent 2,929,804, March 22, 1960.

[5] Sheth, J. P.; Klinedinst, D. B.; Wilkes, G. L.; Yilgor, I.; Yilgor, E. Polymer 2005, 46, 7317 – 7322.

[6 Das, S.; Yilgor, I.; Yilgor, E.; Inci, B.; Tezgel, O.; Beyer, F. L.; Wilkes, G. L. Polymer 2007, 48, 290 – 301.

[7] Sherman, A. A.; Hamer, C. E.; Lucast, D. H.; Augustine, T. E.; Winkler, W. J. U.S. Patent Application 2009/0036598.

[8] Rinaldi, R. G.; Hsieh, A. J.; Boyce, M. C. J Polym Sci: Part B: Polym Phys 2010, 49, 123 – 135.

[9] Jewrajka, S. K.; Kang, J.; Erdodi, G.; Kennedy, J. P. ; Yilgor, E.; Yilgor, I. J Polym Sci Part A: Polym Chem 2009, 47, 2787 – 2797.

[10] Erdodi, G.; Kang, J.; Kennedy, J. P.

J Polym Sci Part A: Polym Chem 2010, 48, 2361 – 2371; and previous publications in this series.

[11] Kang, J.; Erdodi, G.; Kennedy, J. P. Thermoplastic Elastomers Magazine International, Volume 2, Issue 4, October 2010, 227 – 230.

[12] Ummadisetty, S.; Kennedy, J. P. J Polym Sci Part A: Polym Chem 2008, 46, 4236 – 4242.

[13] Kang, J., Erdodi, G., Kennedy, J. P., Rendering polyureas melt processible.

J Polym Sci Part A: Polym Chem, 2011, 49: 2461 – 2467.

[14] Kang, J.; Erdodi, G.; Kennedy, J. P.; Yilgor, E.; Yilgor, I. J Polym Sci Part A: Polym Chem 2009, 47, 6180 – 6190.

[15] Kang, J.; Erdodi, G.; Brendel, C. M.; Ely, D.; Kennedy, J. P. J Polym Sci Part A: Polym Chem 2010, 48, 2194 – 2203.

[16] Lu, M. G.; Lee, J. Y.; Shim, M. J.; Kim, S. W. J Appl Polym Sci 2002, 85, 2552 –2558.

[16] Awad, W. H.; Wilkie, C. A. Polymer 2010, 51, 2277 – 2285. 

A more detailed account of this research has been published in Journal of Polymer Science Part A: Polymer Chemistry, vol.

49, issue 11, p. 2461 – 2467, 1 June 2011 (see [13]).

With HACE

Without HACE Fig. 7:  Idealized micromorphology of conventional (without HACE) and HACE-containing polyureas. the formulas under the sketches indicate H-bonding: strong bidentate H-bonds in conventional (no HACE) polyureas result in elevated tflow and prevent melt processibility (left); H-bonds arising in the presence of polycarbonate- and polyether-based HACEs are loser, which flexibilizes the hard segments and renders the products melt processible (right).

H

H

N

N

N

H O H

O H

H

N

N O

PIB soft segment Composite hard segment H-Bonds (DI-CE)n HACE

N

N

O

O O

H O H N N

N

H O H O

O H O H N N

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

PDA Europe 5th ANNUAL CONFERENCE 14 - 16 November 2011 HOTEL BEL AIR THE HAGUE, HOLLAND JOIN US FOR ANOTHER SUCCESSFUL EUROPEAN POLYUREA EVENT !

SUBMIT A PAPER By presen ng a paper at this conference, you provide your organisaon with invaluable industry visibility, gain recogni on amongst your peers, and reinforce your exper se within the POLYUREA community.

Papers and case studies are invited from polyurea coa ng professionals - from raw material suppliers to applicators (in English).

Abstract Submission deadline: 30 August 2011 For more details and submission condi ons, please visit our website: www. pda-europe.org

Educa on Course: « Introduc on to Polyurea for the Applicator and the Contractor » Physical proper es of polyurea, tes ng procedures, surface prepara ons, applica on procedures and techniques, and advances in and types of equipment.

When? 14 November, 08:30-12:30h

Live demonstra ons

Surface Prepara on Course: « PDA Europe Metal Surface Prepara on Course » ♦ ♦

Extended 4-hour advanced course More details on surface evalua on and prepara on techniques supported by prac cal demonstra ons ♦ Must see for applicators new to industry or those fine-tuning their techniques When? 14 November, 14-18h

During educa onal courses on 14 November and during the Conference on 16 November.

Case studies & presenta ons Latest developments and news of the polyurea industry When? 15 & 16 November

Table top exhibi on Great opportunity to promote your company and products to a wide audience, as well as network with European and interna onal industry representa ves.

When? 15 & 16 November

Registra on will be open shortly - check www.pda-europe.org for details or contact PDA Europe at info@pda-europe.org / +32 2 761 16 11 PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

243

B. W. Naber, G. Behrendt*

Recycling flexible foam PUR – part 4 – thermal recovery

of the PUR-FF a release of any climate related or ozone layer depleting gases that have been used as blowing agent is not to be feared, because in general they have already escaped during manufacturing.

Polyurethane flexible foam materials (referred to here as PUr-FF) are susceptible to all sorts of contamination, because of their open cell structure, making working with used PUr-FF seem questionable on the grounds of hygiene alone. Direct material recycling or recycling as a raw material is possible for off-cuts and waste from production. Used PUr-FF can sensibly only be incinerated preferably in an energy recovery plant. the share of PUr-FF in total household and industrial waste is small. However, problems can occur in thermal recovery and they are reviewed in this paper. they are essentially caused by the low density of these products. Various possibilities for direct and indirect thermal recovery are described and discussed in conclusion.

This leaves as the last and only way of recycling used PUR-FF, is really only incineration, if possible, recovering the energy content in accordance with directive 2008/98/EU and the AbfKrwG. Since no plastic can be subjected to an endless recycling process loop because of the property losses at each step, the final stage of use is necessarily thermal energy recovery in a modern incinerator or waste fired power plant.

1. Introduction

There is a variety of publications dealing with the flammability and the burning behaviour of plastics, including PUR-FF. The book by G. Beilicke, Structural fire protection/fire exposure/heating values for calculation, ISBN-10: 3-329-00650-1 deserves mention here. DIN 18230-3 of August 2002 gives information on the lower calorific value Hu or H of plastics and plastic composites. The BASF SE definitive brochure of 12 July 2010, “Flame retardant engineering plastics” (with 50 references), gives detailed information on the flammability of plastic materials, test methods and requirements in various application areas (such as construction, automotive, aerospace).

PUR-FF are highly refined products coming from petroleum chemistry and this means both the polyol component, whether polyester (PESOL) or polyether (PETOL), and the isocyanate component (toluene diisocyanate TDI or polymeric diphenyl methane diisocyanate pMDI). As already stated in part 1, PUR-FFs are thermosets, meaning they cannot be melted. This eliminates all recycling processes that are common for other (thermoplastic) bulk plastics.

Because of their open cell structure PUR-FFs have a strong tendency to absorb contaminants from the surroundings (“breathing effect”), whether they are organic or inorganic dust, water, microorganisms, or residues from dried fluids in the widest sense. Issues of hygiene are not the least of the problems impeding complete recycling of this group of materials. The many possible different ways offered by PU chemistry of giving a plastic certain properties, is another difficulty, which presents almost insurmountable problems to the recycler. There is no existing way, how-

* 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

244

ever imaginable, of collecting and recycling unmixed used PUR-FF. PUR-FF based on renewable raw materials (e. g. OH-functionalised natural oils) and certain copolymers used in polyurethane PUR-FF (polymeric polyols based on PETOL grafted with styrene and/or acrylonitrile) further complicate the problem.

Other flexible foams that have not been produced on polyurethane basis such as rubber, latex, PP etc. must be carefully separated, before any recycling process, whether direct material or raw material. This condensed list of problems in recycling PUR-FF shows that only clean, pure production residues and waste materials that are available in sufficient quantity are amenable to recycling.

Dumping in a landfill site would be possible in principle, as essentially fully reacted polyurethanes are inert in landfills or biodegrade into environmentally friendly products (own investigations, TU Berlin).

That the seemingly large volume of this class of material is an obstacle to the use in landfill should be put into perspective, when the easy compressibility of PUR-FF under the pressure of subsequent waste layers in the landfill is considered and noted that a foam of the (usual) density 30 kg/m3 only contains 3 % (volume) of plastic and consists of about 97 % by volume of air. Dumping plastic waste in landfills is no longer permitted under the European Union waste law (directive 1999/31/EU). With the open cell structure

The book by J. Troitzsch, “Plastics Flammability Handbook – Principles, Regulations, Testing, and Approval”, 3rd edition, Carl Hanser Verlag, Munich, Vienna, 2004, ISBN-10: 3-446-21308-2, is a standard reference.

K. W. Kroesen describes the combustion of polyurethane including PUR-FF, in detail in the book by W. Rasshofer, “Recycling of polyurethane plastics”, Carl Hanser Verlag, Vienna, Munich, 1995, ISBN 3-929471-08-6.

It should, however, be noted that the fire behaviour of plastics in buildings and vehicles is not comparable with their behaviour in waste material incineration plants.

In the following discussion, the behaviour of PUR-FF in the various types of industrial thermal processing plants is described.

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

2. Incineration of PUR-FF 2.1 Importance of incineration in the disposal of PUR-FF waste The proportion of plastics in the total household waste amounts to about 9 % by mass (Isopa fact sheet “Energy recovery from flexible PU foams”, June 2001). Setting this quantity equal to 100 %, that means 3 mass% of polyurethane and 97 mass% of other plastics. The proportion of flexible foam in the PUR fraction is about one-third, or only 1 % of the total mass fraction of plastic. It should be noted that this figure is only an average. For non hazardous industrial waste and bulky waste (upholstered furniture), the proportion may well be in two digits.

A waste stream containing high proportions of (crushed) PUR-FF, mixed with wood, other

plastics, petroleum oils and paint residue is the shredder light fraction (SLF) from the recycling of old cars. Dismantling old cars has been promoted for many years, but has proven to be an economic mistake and is now continued only for the purpose of cannibalising. SLF is such a complex waste stream that, even with the best intentions, only thermal disposal makes sense. There have been studies and work to make this stream into a usable material. That was and is a waste of time and money. Even subsidies granted for such work, from whatever source, change nothing.

Although the quantity of PUR-FF under discussion here appears marginal, its’ treatment in waste incineration plants is not easy and certainly worth further consideration. It is not important which type of PUR-FF is to be disposed. In a fire they are all (almost) the same.

2.2 Combustibility PUR-FFs, which have been produced only from polyol and isocyanate are combustible materials whose behaviour during combustion depends on many factors. Such influences are: • the density of the foam (the lower it is, the higher the burning rate) • the size of the particles fed to the combustion chamber • the air supply • the oxygen content in the combustion air • the impurities level, especially water.

Foams ignite and burn very quickly thanks to their large surface area. In many cases, however, PUR-FFs contain varying quantities of flame retardants. These can be both liquid products, such as tris-(chloroethyl) phosphate TCEP and tris-(chloropropyl) phos-

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phate TCPP, and solid compounds such as ammonium polyphosphate, melamine or aluminium hydroxide. In these cases, the foams ignite more slowly and their combustion is inhibited. This property, however, plays only a minor role under the conditions of an incineration plant. Shortly before ignition, the foam melts and collapses with decomposition. The mainly gaseous decomposition products ignite and the heat produced supports the propagation of combustion. As PUR-FF consists of carbon C, hydrogen H, oxygen O, and nitrogen N, the combustion gases contain mainly carbon dioxide CO2, carbon monoxide CO, oxides of nitrogen NOx, and water H2O depending on the temperature and oxygen supply. As flame retardants are often present, the flue gases still contain hydrogen halides HX (X = Cl, Br) and phosphorus oxides and occasionally sulphur oxides SO x. In the absence of oxygen saturated (methane, ethane, etc.) and unsaturated hydrocarbons (ethene, ethyne, propene, etc.), traces of hydrogen cyanide (hydrocyanic acid, HCN) and a variety of other compounds are formed. A downstream multi stage combustion flue gas scrubber is mandatory (17. BimSchV). PUR-FF produced only from polyol and isocyanate has an ash content of < 0.2 %. Products with inorganic flame retardants or additives may well show ash contents of 20 % or more. No increased formation of dioxins in the flue gas could be detected in studies at the Tamara pilot plant in Karlsruhe (Isopa). Different calorific values are quoted for PUR-FF in the literature.

They are all around 5.3 kWh/kg (approximately 25 MJ/kg) and similar to values for hard coal. The discrepancies are easily explained by differences in the PUR formulation and the content of fillers and additives (for example PUR-FF B3, in a wire basket: 6.4 kWh/kg PUR-FF B3, with wood (upholstered furniture): 5.3 kWh/kg according to H. Schaller, lecture at the 9th Schwerin science day, 10.09.2004).

In practice, the water content plays an important role, as water may be present both as a liquid in the foam cells, and also physically dissolved in the polymer matrix, which is particularly the case in viscoelastic

246

PUR-FF. Mechanical impurities also play a role in thermal recovery. Inorganic contaminants will reduce and mineral oils will increase the actual calorific value.

2.3 Technology PUR-FF will, in almost every case, be burned in a mixture with other wastes, such as household rubbish or commercial waste. A mono-incineration should be possible with specially designed furnaces and appropriate fire management, but then the problem arises of collection and delivery of sufficient foam quantities, to allow the continuous operation of such facilities economically. A large enough inventory for several days of operation is probably not economically sensible because of the large volumes this would entail as a result of the bulk density, even after compression into bales of > 100 g/l density.

Compressing PUR-FF for transport is possible, but only customary when this is to bring it to a further value-added process, as is the case in shipping block foam blends for use in the production of composite foams. Shipping bales to incinerators does not make economic and environmental sense, especially over long distances, (because of the large amount of carbon dioxide emitted by the transporting vehicles relative to the mass transported). Mono-incineration of plastic waste requires specially designed furnaces that are easiest to make when designed as fluidised bed plants, because, among other reasons, of the high calorific value and the behaviour during combustion (melting coking). Successful tests have been carried out in Japan (Isopa).

2.3.1

Crumbing

In any event, and for each recycling process including combustion, the first step is grinding the PUR-FF to the particle size appropriate to the process. Grinding to particles of 5 – 15 cm diameter is satisfactory for combustion, without laying too much emphasis on particle size or shape. Low speed granulators are suitable machines, because their energy consumption is acceptable and noise

levels are low. In all cases, the crumber has to tolerate, the presence of (for example, foam coated) metal wires, springs or structural parts. Hammer mills and screw grinders can also be chosen, in many cases, as grinding machines. The choice of these units is always dependent on the nature and composition of the waste stream being fed to the incinerator. Crumbing should take place directly before introduction into the furnace to avoid the need for large scale storage capacity due to the low density of foam.

2.3.2

Hearth incineration

The mixed waste stream is fed to a conventional fire hearth. The particular design of this is not very critical. It has been found by experiment that the proportion of PUR-FF in the waste stream should not exceed 10 % by mass. 3 mass%, corresponding to about 30 % by volume of the burning mixture, is a safe level to assure trouble-free combustion.

PUR-FF must in all cases be crumbed. Too large crumbs cause holes in the ember bed by their extremely fast burn, through which the combustion air blows and reduces the burning effect of the still burning material.

This reduces the energy yield, and the resulting ashes still have a high proportion of unburned carbon fractions. In addition, the oxygen content of the combustion gas rises above the limit of 17. BlmSchV. The ignition loss, LOI, is then too high to be permitted for landfill. The low density of uncrushed PUR-FF pieces brings the possibility that they may be carried away by the burning gases and then remain hanging, still burning, in the filter stage, car seat cushions and mattresses are particularly critical in this regard. A limiting factor in the use of PUR-FF is the chlorine content, which may not exceed 1.5 % by mass of material fed to the incinerator.

PUR-FF can contain a significant quantity of chlorine Cl (and bromine Br) from the included flame retardants. During the combustion of collective plastic fractions, however, the chlorine content of PVC is expected to exceed significantly that of PUR-FF. In this fraction hydrogen fluoride HF in the exhaust gases from PTFE (“Teflon”) can lead to additional problems. Hydrogen halides HX (X = Cl, Br, F), formed during the incineration

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

process can have a very corrosive effect on the conventional furnace lining and render the flue gas scrubber ineffective.

2.3.3

cally the plastic waste to be used, to mix it and to prepare it. PUR waste can easily be mixed into the fuel stream after appropriate conditioning (Isopa).

Rotary kiln 2.3.5

Gasification

Experiments in France showed that about 15 % by mass of shredder light fraction (SLF) can be added as co-fuel with household waste, without compromising stable combustion or exceeding the flue gas limits (Isopa). Also here one of the limiting parameters is the chlorine and other halogens content.

Plastic waste, even when it contains PUR-FF, can be subjected to a gasification process in a mixture with coal dust. The aim of this process is the production of combustible gases to run steam boilers or gas engines, or synthetic gas for producing methanol or hydrocarbons (after Fischer-Tropsch).

2.3.4

Known processes are:

Cement manufacturing

Mixed plastic waste can be used, after appropriate treatment (PVC separation, grinding, granulation/compaction) as a co-fuel for cement production. In experiments in Unterfaz, Switzerland, up to 16 % by mass of the primary fuel could be replaced by plastic waste. It was found here that a reduction in emissions of NOx and SOx occurred. Such a procedure requires, however, that the secondary fuel should satisfy exact quality requirements (crumb size, chlorine content < 0.1 %). Successful energy recovery depends strongly on the efficiency of the collection system and the ability to sort specifi-

• • • •

the fluidised bed gasification the slag bath gasification the fixed bed pressure gasification the multi-bed shaft gasification (according to H. Schalles, the most modern system)

Plants have been in operation in Schwarze Pumpe, Germany, that worked successfully according to these procedures. The low price of methanol in the period 1995 to 1997 made them no longer economically viable. Using the resulting gas as a source of energy, failed because of the price for these gases, after preparation and purifica-

tion, in comparison with natural gas. According to H. Schalles (lecture at the 9th Schwerin science day, 10.09.2004), the overall efficiency of the recovery facility is > 87 %.

The gases produced are used for both power generation through block heat and power plants and through fuel cells. The chlorine content is critical in every case. It should not exceed 0.5 % by mass. Whether this technology can be revived in the future in the light of the ever increasing scarcity of fossil fuel resources is uncertain. In addition, the use of plastic waste alone in the pressure gasification process does not give stable conditions and therefore about 30 % by mass of brown coal had to be added.

2.3.6

Reducing agent in blast furnaces

Plastics, including PUR-FF, crack immediately into carbon monoxide, CO, and hydrogen, H2, at the temperatures prevailing in the reduction zone of a blast furnace, 1,500 – 2,000 °C. These gases act under the conditions obtaining as a reducing agent for iron ore. The PURFF can contain up to 1.5 % by mass of chlorine (Stahlwerke Bremen AG, 2000). However, for technical reasons it must be compressed (“compacted”). Up to 30 % of primary fuel can be saved through the use of plastics as a

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reducing agent. PUR-FF, similarly to all condensation polymers, is not ideal for this application because of the high oxygen content in the polymer, as the carbon should be available solely for reducing the ore.

2.3.7

Carbonising

Carbonising is defined as combustion under a lack of oxygen. The aim is to extract gases that are useful for heating the carbonising cell and liquids, that should be normal refinery products (“syncrudes”). The method has been tested under different conditions and with different raw material (plastic) mixtures. It has, however, not become established for technological and economic reasons. Proportions of PUR-FF did not disrupt the process.

It was, anyway, clear from a very early stage that very tight limits are placed on any conceivable used plastics recycling. It is not possible to send everything, certainly not all plastics, for recycling, without allowing thermal recycling in the most modern plants with recovery of the energy content. To denigrate modern systems of this type as either “polluters” or “dioxin scatterers” is not helpful and reflects the serious lack of knowledge of technological processes (incidentally incinerators are dioxin reducing!). The production and use of plastics and, in particular, foams is generally the most valuable possible recycling of crude oil, if thermal exploitation after use is allowed, that is, the use of the polymer’s energy content.

Comparing the ecological balance of:

2.3.8

Hydrogenation

Plastic waste, including PUR, as well as PUR-FF was reductively cleaved in the Bottrop coal oil plant. The process principles are the classic coal chemistry process of Fischer-Tropsch and Bergius. The aim of the process is the extraction of hydrocarbons whose molecular mass and hence properties can be adjusted from light naphtha to heavy fuel oil by changing the process parameters. The plant has since been shut down. In addition to the chlorine content the oxygen content in PUR and other condensation polymers is a disrupting factor, since this results in increased hydrogen consumption. Similar plants are operated on pilot plant scale in China and the US (VDI news 25.05.2005: “High oil price revives coal liquefaction”).

3. Technical philosophical observation The recycling of plastic waste is a path that has been followed since the early days of plastics processing. There have always been waste and off-cuts from plastics processing that were recycled directly into the manufacturing process at the processing plant. There has been and is a large number of sophisticated technical solutions for this (e. g. trimming machines, granulators, compactors).

248

• (material) production scrap recycling, • (material) recycling collected used plastics (e. g. DSD, “yellow bag”), • thermal recycling with energy recovery, material recycling of used plastics comes out as by far the most unfavourable.

Collection, transport, sorting, cleaning and granulation waste every economic and environmental advantage. This path, therefore, has nothing, absolutely nothing, to do with the widely praised conservation of resources (“sustainability”). The consumption of the precious resource water, alone, is several times higher than in the production and processing of new material, not to mention the increased energy consumption, which is often higher than in primary production.

Separating the high calorific content plastics fraction from household waste ensures that the contents of the “residual waste bin” no longer burn independently in the incinerator, but can only be disposed of through firing by an auxiliary oil or gas burner. That is oil or gas from which, inexpensive, highest quality, new plastics could be produced by highly effective large-scale processes. This assessment also clearly follows the EU Commission directive 2008/98/EC, that updates the definition and harmonisation of waste management in the EU, in which waste separa-

tion is no longer mandatory and energy recovery is no longer demonised. This directive has not previously been implemented in federal German law, because lobbyists such as the BDE obviously oppose it, because of the possible loss of subsidies. Consequently the federal republic of Germany has been warned by the EU Commission. The directive should now be implemented into German law by the end of 2011.

If one considers the fact that 86 % of the crude oil produced goes directly to energy use, that is to say, burning (heating oil, fuels), and only about 4 % is converted into polymers (Isopa fact sheet, “Energy recovery”, June 2001) (the remaining 10 % serves as chemical raw material in, for example, cosmetics, household chemicals, pharmaceuticals, agrochemicals, construction), it is clear that the discussion about the usefulness of recycling is a phantom debate or an ideology. Even the argument about providing thousands of jobs is only partially sustainable, as all these jobs are highly subsidised.

It should no longer be possible to argue along these lines today. Here the sweet poison of subsidy has already had a permanent effect. So what is against including PUR-FF in the thermal recovery of waste plastics?

The 21st century will be the century of plastics, just as the 20th century was the century of steel and the 19 th was the century of steam. Every innovation of the last few decades is both unthinkable and unfeasible without plastics, be it modern cars, batteries, telecommunications systems and equipment or alternative methods of energy production.

The earth that will surpass the 7 billion population mark in 2011, can only be kept inhabitable, if we are careful with our resources.

Plastics will make their growing contribution.

PUR-FFs are emphatically included in this development. There will always be crude oil or other fossil hydrocarbon resources (shale oil and tar sands, coal, etc., even carbon dioxide from the atmosphere) for the production of polymers! Efficient, environmentally sound thermal disposal plants using the cleaning power of fire to produce energy, are indispensable in this respect. 

PU MAGAZINE – VOL. 8, NO. 4 – AUGUst/sEPtEMbEr 2011

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DISTRIBUTION-NETWORK Color Paste, IMC, Release Agents, Blowing Agents, Spray Systems, TPU Tel: +39.0522.693774 Fax: +39.0522.745506 Cell: +39.3482607526 Mail: pbalboni@distribution-network.it Web: www.distribution-network.it

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Im Mßhlenfeld 5 31008 ELZE ¡ Germany Phone 00 49 / 50 68 / 925 - 0 Fax 00 49 / 50 68 / 925 - 25 Email info@ISO-ELEKTRA.de Internet www.ISO-ELEKTRA.de KlÜckner polyPUR Chemie GmbH Vinckeweg 15 ¡ 47119 Duisburg ¡ Germany Phone: +49 (0) 203 50039-0 ¡ Fax: -39 info@polyPUR.de ¡ www.polyPUR.de

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Sonderhoff Chemicals GmbH Richard-Byrd-StraĂ&#x;e 26 50829 KĂśln¡Germany Tel +49 221 95685-0¡Fax +49 221 95685-599 info@sonderhoff.com¡www.sonderhoff.com

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PUR-Systems GmbH & Co. KG 46 avenue des Allobroges BP 116 â&#x20AC;&#x201C; 26103 ROMANS CEDEX â&#x20AC;&#x201C; France Tel. +33 4 75 72 72 75 ¡ Fax +33 4 75 02 11 73 E-Mail info@baule.com Internet www.baule.com

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Foam Supplies, Inc. 4387 N. Rider Trail Earth City, MO 63045 Phone +1 (800) 325-4875 toll free Fax +1 (314) 344-3331 Email: tkeske@foamsupplies.com www.foamsupplies.com www.ecomatesystems.com

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251

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Machines Gear pumps MANUFACTURING OF MIXING AND DOSING MACHINERY ulitsa Gvardeyskaya 190, Tsurupinsk, Khersonskaya oblast, 75101, Ukraine Telephone: +380 67 553-95-79 E-mail: info@osv.com.ua Internet: www.osv.com.ua

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RAMPF Dosiertechnik GmbH & Co. KG Römerallee 14 D-78658 Zimmern o.R. T +49 (0) 741 2902 - 0 F +49 (0) 741 2902 - 2100 E info@rampf-dosiertechnik.de www.rampf-dosiertechnik.de

Flow measurement Zweigniederlassung der Oerlikon Textile GmbH & Co. KG Geschäftsbereich Pumpen Leverkuser Straße 65 · 42897 Remscheid · Germany Phone +49 (0)21 91 67-1814 · Fax +49 (0)21 91 67-1794 pumpsales@barmag.de · www.pumpen.barmag.de

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LACKFA Isolierstoff GmbH + Co. KG Industriestraße 2 25462 Rellingen · Germany Phone: +49 4101 3916-0 Fax: +49 4101 3916-16 Email: info@lackfa.com - www.lackfa.com

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H & S Anlagentechnik GmbH Sandstraße 19, 27232 Sulingen, Germany Phone +49 4271 1011 · Fax +49 4271 2576 E-mail: info@hs-anlagentechnik.de www.hs-anlagentechnik.de

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Kracht GmbH Gewerbestrasse 20 58791 Werdohl, Germany fon: +49 (0)2392/935 0 fax: +49 (0)2392/935 209 mail: info@kracht.eu web: www.kracht.eu

THE FOUNDATION FOR SUCCESS STORAGE TANKS PRODUCT HANDLING PROCESSING FACILITIES DISCHARGING UNITS PROCESS AUTOMATION RENEWABLE ENERGIES

Hans-Jürgen Keil Anlagenbau GmbH & Co. KG Zum Welplager Moor 8 49163 Bohmte-Hunteburg, Germany Tel.: +49 5475 9200-0 Fax: +49 5475 9200-190 Wwww.keil-anlagenbau.de

253

Publication information & contacts

Services Elastomers, polyurethanes, TPE â&#x20AC;&#x201C; development, testing, failure analysis

Dr. Joop Koster Eddy Vanstraelen Free-lance sales representative PU-system development consultant Mobile +32 48 63 11 745 E-mail eddy@evspolyservice.be

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Kracht GmbH Gewerbestrasse 20 58791 Werdohl, Germany fon: +49 (0)2392/935 0 fax: +49 (0)2392/935 209 mail: info@kracht.eu web: www.kracht.eu

KRAL AG, Bildgasse 40 Industrie Nord, 6890 Lustenau, Austria Tel.: +43 / 5577 / 8 66 44-0 Fax: +43 / 5577 / 8 84 33 www.kral.at, E-Mail: info@kral.at

Testing, calculation, analysis, development, consultancy, sampling Contact: Dr Markus Grass +49 (0) 62 01 80 51 23 markus.grass@freudenberg.de

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Freudenberg Forschungsdienste KG 69465 Weinheim / Germany www.forschungsdienste.de

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High precision ďŹ&#x201A;ow measurement VSE Volumentechnik GmbH HĂśnnestr. 49 58809 Neuenrade / Germany Phone +49 (0) 23 94 / 6 16 30 Fax +49 (0) 23 94 / 6 16 33

Sonderhoff Services GmbH Mathias-Brßggen-Str. 126-128 50829 KÜln¡Germany Tel +49 221 956526-0¡Fax +49 221 956526-39 info@sonderhoff.com¡www.sonderhoff.com

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PU MAGAZINE â&#x20AC;&#x201C; VOL. 8, NO. 4 â&#x20AC;&#x201C; AUGUst/sEPtEMbEr 2011

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