Speciality Chemicals Jul 2010

Direct routeDrop-in bio-basedalternatives

Fuel circleBiorefineries of the future

Direct routeDrop-in bio-basedalternatives

Fuel circleBiorefineries of the future

Agrochemical intermediates ... Leather &textile chemicals ... Electronic chemicals ...Osmium chemistry

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JULY 2010Volume 30 No. 07

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Regulars

Editor’s letter 4

News 6

Forthcoming events 41

Agrochemical intermediates

Shackles on innovation 11Agrochemical innovation is more necessary than ever, yet has never beenmore costly and difficult to do. We report from Informex USA 2010

Simply the pest 14Are we on the verge of a new kind of chemistry in pest control? ElisabethJeffries reports

More from less in agrochemicals 16Dr Susan Brench and Dr Chris Rainford review how Pentagon Chemicalsstreamlines the introduction of new agrochemical products and optimises theperformance of existing processes

Leather & textile chemicals

So long, solvents 18Plasma technology is perfect for giving fabrics a water-repellent nano-coating, so why is the textiles industry only just beginning to see its value, asks Emma Davies?

Eco & economical advantages of anti-soiling leather protection 20Dr Michael Franken of Lanxess looks at the thinking behind the Aquaderm X-Shield technology

Electronic chemicals

Additives for copper electroplating in microelectrons 24Dr Marco Arnold and Dr Cornelia Röger show how BASF develops key compounds for even smaller node sizes

Developments in chemistry for printed electronics 27Dr Peter Harrop of IdTechEx takes a brief look at the role of the chemicalsindustry in the next electronic revolution

Sustainability

Keeping things going 29Sustainability was the theme of Wacker Chemie’s international press briefing earlier this year

Getting to the point 32Dennis McGrew of Genomatica outlines the case for directly produced, drop-in bio-based replacements for traditional manufacturing methods

Designing the next generation of biorefineries 35Professor Franck Dumeignil of the Université Lille Nord de France presents the concept and the objectives of the EuroBioRef project

Osmium chemistry

Reactions & scope of osmium chemistry: An overview 38James Thomson of Ceimig looks at the chemistry of the heaviest of the metallic elements

Outsourcing Special

Publication– Bound between pages 22 & 23

Volume 30 No. 07

Speciality Chemicals Magazine July 2010 3


29Sustained effort

18Making a splash

14Flower power

In the September issue of Speciality ChemicalsMagazine

• Pharmaceuticalintermediates• Flame retardants• Microencapsulationtechnology• Water & paperchemicals

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Contents_p03_scm07_Contents 7/14/10 9:54 AM Page 3

Following the worst economic crisis in living memory - even

allowing for the fact that living memory seems to amount

to about five years among the bankers who got us into this

mess and subsequently arranged it that everyone else could pay

their way out of it - there could only be one direction to go in.

After all, life went on, most of us still work, earn and consume.

It was inevitable that at some point some common sense would

find its way back into Western society after the panic. Just as

inevitable, in fact, as that manufacturing industry would take

more than its fair share of the pain and less than its fair share of

the rewards. Some things don’t change.

The mood has generally been much better since one of the

latest and most glorious springs Europe has enjoyed in decades.

(Maybe not entirely a coincidence? Just a thought.) The indica-

tions for the chemicals industry have also been much more pos-

itive, both in terms of the predictions put out by industry bodies

and the views of the financial markets.

In June, CEFIC put out its forecasts for growth in the chemi-

cals industry, pharmaceuticals omitted, over the next 18 months.

After the staggering slump in demand from Q4 2008 into 1H

2009, it said, demand had already seen “an equally sharp

rebound” in 2H as the previous liquidation of supply chains was

reversed, though this was nowhere near enough to make up for

the previous drop. Overall, 2009 saw a fall of 11.3% in output.

The recovery in output levels continued in early 2010 at a rate

well in excess of what CEFIC itself anticipated when it had looked

at trends in November 2009. This is likely to continue well into

the year. Overall, CEFIC forecasts year-on-year production

growth of 9.5% this year.

For 2011, however, growth is forecast to fall sharply back to a

more modest 2%. CEFIC warned that the recovery still looks frag-

ile and that capacity utilisation within the industry still remains

below normal levels. The industry would be vulnerable to any

economic shocks arising from external factors, most worryingly

the prospect of sovereign debt defaults.

To look at in a wider perspective, from its peak of 110.5 (based

on the year 2005 = 100) in Q1 2008, the fall to the trough in Q1

2009 was a staggering 20.2% to 88.2. The following 14.9% rise,

to 101.3 in Q1 2010, still means that the industry is barely back to

where it was in 2005 and will probably not reach 2008 levels

again before 2013.

Both decline and rebound were sharpest at the commodity

end of the market. Basic inorganics, polymers and petrochemicals

saw falls of 18.5%, 16.4% and 8.9% respectively in 2009, fol-

lowed by projected rebounds of 11.0%, 14.5% and 11.0% in

2010. For speciality chemicals, there was an 8.2% fall followed by

a 8.5% rise. This sector, however, is forecast to see relatively

strong 2.5% growth in 2011.

At more or less the same time, Moody’s Investors Service con-

firmed a stable outlook for the chemicals industry, which, it said,

is “in a sustained rebound in Asia, Europe and the Americas”,

aided by improving demand, low raw materials prices and strong

balance sheets. Credit conditions are reasonably good and likely

to remain so.

Moody’s industrial production figures for Europe differ very

sharply from CEFIC’s - 2.3% growth this year, rising to 3.4% next

- though the terms of reference are probably somewhat different.

They are also well below what was projected for the US: 4.3%

this year, falling to 4.1% next.

Moody’s also expected M&A activity in the industry to rise

substantially in 2010. True, it was unlikely to go any lower after

such a quiet year, but this view has been echoed by other lead-

ing analysts, such as Peter Young of Young & Partners and

Dmitry Silverstein of Longbow Research.

More interestingly, many believe that a disproportionate

amount of the deal-making would take place in speciality chemi-

cals. The sector is less capital-intensive than basic chemicals and

more affected by raw materials costs, which typically account for

60-80% of the cost-of-goods-sold at speciality chemicals compa-

nies. These have been a relatively benign factor since the slump

took the sting out of previous hikes.

Moreover, as we documented in the April edition of SCM,

even while delivering eye-wateringly bad results for last year, spe-

ciality chemicals companies have become rather good at conserv-

ing cash. Many generated record free cash flows in 2009, some

of which has been used to pay down debt. Some of the rest must

be available for acquisitions - and not just at the fire-sale prices

that prevailed sometimes last year.

Right on cue, as we report this month, BASF has since agreed

to buy Cognis in a deal that appears well-priced on both sides

(page 6) and which - unusually - was well received, even in the

short term, in the financial markets. Ironically, this will be the last

of the major buys initiated by CFO Kurt Bock, who will became

chairman of the management board next year.

What next? The process by which two industry behemoths,

BASF itself and Dow, have transformed themselves into mainly

speciality players is substantially complete although some of the

latter’s commodity businesses still have ‘For Sale’ sign notices out.

Who will drive forward the next wave of transformations that will

reshape the industry?

And what will be the role of private equity? For some time dur-

ing the downturn when cash was king, the companies who once

seemed poise to take over the industry appeared a spent force.

Now there are signs that they are back.

May saw the takeover of Mallinckrodt Baker by New

Mountain Capital. And, more unusually still, even the labour

unions, who often (correctly) regard private equity as asset-

sweaters, were enthusiastic. Of course, it might not have hap-

pened but for the chance that Dow had made the former CEO

of Rohm and Haas available to New Mountain - but this is, as we

all know, a small world.

Dr Andrew Warmington

Editor - Speciality Chemicals Magazine

Editor’s letter

Out of the woods?There are many positive indicators, but is it too soon to talk of recovery?

“The indicationsfor the chemicalsindustry ingeneral have been much morepositive, both interms of theforecasts put outby industry bodiesand the views ofthe financialmarkets.”


4 July 2010 Speciality Chemicals Magazine

Editors_letter_p04_scm07_Editors_Letter 7/14/10 9:58 AM Page 4

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News



BASF acquires Cognis for €3.1 billionGERMANY

BASF has agreed to acquire Cognisfrom Permira Funds, GS CapitalPartners and SV Life Sciences for anequity purchase price of €700 mil-lion in cash, €503 in pension obliga-tions and extra debt to give a totalenterprise value of €3.1 billion, or7.3 times EBITDA. This should becompleted by November, subject toregulatory approval.

This acquisition continues BASF’srecent strategic move from commod-ity to speciality chemicals, as well asadding over 5% to its sales and con-firming it as the world’s largestchemicals company. A sale had beenin the pipeline for some months; thethree funds had tried to sell Cognisin 2006 but failed to secure the pricethey wanted, then considered anIPO only to abandon it as theEuropean stock market slid down.

According to analysts, Cognis’sowners had hoped to get about €3.5billion, while BASF was reluctant topay over €3.0 billion, as it nowbelieves that it overpaid for CibaSpecialty Chemicals last year. €3.2-3.3 billion was widely touted as thelikely range. Lubrizol reportedlyoffered more, but only via a partly-share financed offer that did notinterest the owners, and BASFbecame the preferred bidder.

Cognis employs about 5,600 peo-ple, almost 40% fewer than when itwas spun off from Henkel in a €2.5billion take over in 2001, and hasproduction sites and service centresin 30 countries. It is best known as asupplier of products and servicesbased on renewable raw materialsfor the health, nutrition, cosmetics,detergents and cleaning industries,while also making products for min-ing, lubricants, coatings and agricul-ture.

The Monnheim-based companyhad sales of about €2.6 billion lastyear, with an EBITDA of €322 mil-lion. It recently announced its bestever Q1 results, with volumes backto the pre-crisis levels of 2008, sales10.6% up on Q1 2009 to €728 mil-lion and adjusted EBITDA 76.9% upat €131 million.

According to CEO Antonio Trius,Cognis has “become a leading inno-vative supplier of speciality chemi-cals” in the past nine years. “In par-ticular, our focus on wellness and

sustainability and our expertise inrenewable raw-material based prod-ucts have been our main success fac-tors. We are convinced that there areexcellent opportunities throughcombining the strengths of Cognisand BASF,” he added.

Cognis will eventually be integrat-ed into BASF’s PerformanceProducts segment, which had salesof €9.4 billion in 2009. This segmentincorporates the Dispersions &Pigments, Care Chemicals,Performance Chemicals and PaperChemicals business units, which areunited by the link of “helping cus-tomers to improve their productsand processes”.

BASF expects to spend €200-250million on integrating Cognis butsaid that it will make savings of atleast €129 million/year. Externalanalysts estimated potential syner-gies at €80-100 million/year. Thecompany aims to achieve at least a20% margin in PerformanceProducts by 2012. No detail has yetemerged about job cuts and plantclosures.

The company’s position in homeand personal care ingredients will beparticularly boosted via Cognis’sstrength in chemicals based on natu-ral raw materials such as palm ker-nels and coconut oil. The CareChemicals division has sales of €3.4billion/year and was already target-ing such areas as hair care, sunscreen and thickeners.

The purchase was well receivedamong financial analyst, giving amild boost to BASF’s shares. PeterSpengler of DZ Bank called the price“reasonable”, adding that “BASF has

a good track record in adding newsegments”.

BASF’s credit rating will probablycome down a notch because of theextra debt it has taken on - an extra€1.9 billion at the end of 2009. Thiswill add to €13 billion in existing netdebt. However, because BASF gener-ates €3-5 billion/year in free cashflow, it does not need to take onextra loans.

This news came only a monthafter BASF announced that CFO KurtBock would succeed Dr JürgenHambrecht as chairman of the boardof executive directors at the nextAGM. Bock had been the architect ofthe €13 billion on purchases BASFhas spent in the past seven years,most notably Engelhard and Ciba,but this will be the last major acqui-sition in the foreseeable future,according to Hambrecht.

Separately, BASF and AstraPolymer Compounding of SaudiArabia are abandoning plans for ajoint venture to produce customer-specific antioxidant blends (CSBs) inthe Middle East. This had been agreedbetween Astra and the PlasticAdditives business of the former Ciba.An existing tolling agreement withAstra covering CSBs is unaffected.

John Frijns, senior vice-presidentfor plastic additives in theEurope/EAWA region, stressed thatBASF is still “convinced of the strate-gic importance of the Middle EastRegion and the need for a local pro-duction unit for customer-specificblends”. However, he said, an evalu-ation of the Ciba legacy had revealednew options that will offer bettervalue to BASF and its customers.

Investment options are now beingevaluated.

Earlier, the Intermediates divisionof BASF had announced that it isworking with RTI International, aresearch institute based in ResearchTriangle Park, North Carolina, todevelop a cost-effective technologyto capture CO2 from waste gasesemitted by coal-fired power plantsand other industrial sources. This issponsored to the tune of €1.6 mil-lion by the US Department ofEnergy as part of its stimulus-fundedinitiative on energy-related researchprojects.

With RTI, which will add its engi-neering and research capabilities,BASF plans to work on novel non-aqueous solvent systems that can berecycled and which would use 40%less energy than conventionalamine-based processes. It alreadysupplies its aMDEA (‘activatedmethyldiethanolamine’) brand oftechnologies to remove acid gaseslike hydrogen sulphide (H2S) andCO2 to some 200 ammonia, naturalgas, syngas and liquefied petroleumgas facilities world-wide.

Since 2007, BASF has worked withRWE Power and Linde in Germanyto develop a process for capturingCO2 from flue gases emitted by coal-fired power plants. These account for50% of all electricity generation and36% of all CO2 emissions in the US.

Finally, BASF is merging its Swissgroup companies BASF OrgamolPharma Solutions and BASF FineChemicals Switzerland to a singlefirm called BASF Pharma (Evionnaz).This is based at the former Orgamolsite in Evionnaz and forms part ofthe BASF Pharma Ingredients &Services Business Unit.

Martin Widmann, general manag-er of the former BASF FineChemicals Switzerland, who hasbeen named president of the newfirm, said that this “reduces com-plexity at our site and simplifiesprocesses”, the two firms havingalready worked together for years.

The former BASF OrgamolPharma Solutions companies atEvionnaz and Saint-Vulbas in Francewere both renamed BASF Pharma inApril. None of the name changes hasany effect on the number of or exist-ing contracts with employees or onrelationships with suppliers and cus-tomers.

Kurt Bock, who masterminded the deal, will be BASF’s next leader

News_p06-10_scm07_News 7/14/10 9:58 AM Page 6

News



In BriefDow Kokam breaks groundDow Kokam, a joint venturebetween Dow and TK AdvancedBattery, has broken ground at thefirst phase of a facility to makelarge-format lithium-ion batteriesfor electric and hybrid electric vehi-cles at Midland, Michigan. This willemploy 320 people and produce600 million watt hours of batteries,supported by a €128 million grantunder the American Recovery &Reinvestment Act. Ultimately, thecompany plans a world-scale,75,000 m2 plant employing 800,with double the current capacity.

Borregaard closes Ravenna Borregaard Synthesis is to close itsBorregaard Italia production plantin Ravenna, with the loss of 40 jobs.This mainly produces catechol andhydroquinone for flavours and fra-grances, agrochemicals, pharma-ceuticals and other industrial appli-cations. The former has been andwill remain in overcapacity, givingthe plant little prospect of returningto profitability, and the companyhad failed to find alternative solu-tions for it.

Aesica buys R5Aesica Pharmaceuticals hasacquired the Nottingham-basedR&D company R5, which developsand manufactures new medicinesand clinical trial materials, particu-larly pharmaceutical dosage forms.This buy, the third in the UK aftertwo large former Big Pharma man-ufacturing sites near London, will“complement Aesica’s existing for-mulations capability and enable itto significantly consolidate andenhance its portfolio of pharma-ceutical and biotechnology clients”,the company said.

Evonik licenses Elevance Elevance Renewable Sciences ofBolingbrook, Illinois, has taken alicence to Evonik Industries’ USpatent portfolio related to metathe-sis technology, not including theCatMETium RF range. It will usethem in its processes to make spe-ciality chemicals, notably oils, lubri-cant additives and antimicrobials,from natural oils such as soybean,canola, corn, sunflowers, palm,rapeseed, algae and Jatropha.Terms were not disclosed.

NETHERLANDS-FRANCE

DSM and Roquette Frères, theFrench-based starch and starch-deriv-atives company, have signed a jointventure agreement for the produc-tion, commercialisation and marketdevelopment of bio-based succinicacid. A new 50-50 joint venture,Reverdia, is being set up in theNetherlands for this purpose.

This follows a co-operationbetween the two firms since early2008 to develop a suitable fermenta-tion technology. Test volumes of theproduct have already been made at ademonstration plant in Lestrem, east-ern France, which was built last year,and have been used in polymers,resins and other products.

DSM subsequently unveiled a tech-nical breakthrough for the manufac-ture of bio-based succinic acid fromstarch that it and Roquette had madeat the 7th Annual World Congress onIndustrial Biotechnology. This, thecompany said, is based on two sepa-

rate innovations, one in enzyme tech-nology and the other in advancedyeast technology.

DSM focused its R&D on a fungalorganism that typically thrives in com-post heaps or on fallen trees, enablingit to find enzymes that are able tobreak down biomass into its con-stituent sugars much more efficientlythan conventional enzymes andwhich can also function at higher tem-peratures. These properties facilitatelower enzyme dosage, better contam-ination control during fermentation,increased feedstock loadings, reducedenergy consumption and shorter pro-cessing times.

Via classical strain improvementcombined with metabolic engineer-ing, DSM claims to have developed anadvanced yeast strain that is capableof converting all of the major fer-mentable six- and five-carbon sugarcomponents in biomass to ethanol,the most common current biofuel.This could double yields compared tothe standard yeasts in use now, which

typically only consume six-carbonsugars and are consequently less effi-cient.

DSM added that is has a totally dif-ferent approach to market develop-ment for second generation biofuels.Instead of remotely producing andbulk-selling enzymes and yeasts, it is“working with customers and partnersto develop more localised, on-site pro-duction”. It believes this to be themost sustainable way forward in thelong run, “because it bypasses longand expensive global supply chainsand truly integrates conversion tech-nology into the biofuel process itself”.

The two companies will expandtheir joint capacity to meet demand,adding that many customers alreadyintend to take shipments from thejoint venture when it starts. The initialfocus will be on products such as 1,4butanediol, polyurethane resins andbiopolymers such as polybutylenesuccinate for applications in paintsand coatings, automotive and textiles,among others.

Bio-succinic acid JV formalisedas new technique is launched

CHINA-GERMANY

Lanxess has announced that its yel-low iron oxide pigments site atJinshan near Shanghai can now runat full capacity of 28,000 tonnes/year. This follows the completion ofanother step in the company’s ‘tech-nical improvement drive’. The com-pany has also revealed that produc-tion of Bayferrox iron oxide pig-ments at its Krefeld-Uerdingen sitein Germany has hit an all-time high

The Jinshan site, which is thelargest yellow iron oxide pigmentsfacility in Asia, opened in 2007.Since then, various different meas-ures have been implemented toincrease production efficiency, suchas consolidating steam generation inone boiler house operation with anadvanced off-gas cleaning system.

In a second phase, which will see€6 million invested up to 2011,Lanxess will further optimise thesite’s environmental protection facil-ities, notably by upgrading thedrainage system. It will also shift thewater supply and the fire-fightingsystem to piping above the ground

for greater availability and easiermonitoring.

Jörg Hellwig, head of theInorganic Pigments business unit,said that Lanxess plans further

growth in the field. “We are confi-dent in the growth opportunitiesoffered by the APAC region andwant in particular to serve risingmarket demand in China for high-quality pigments in the long term,”he added.

Meanwhile, Krefeld-Uerdingen,which at 280,000 tonnes/year capac-ity is the largest of its kind in theworld, produced about 25,000tonnes of Bayferrox in May. Of this,85% was exported. This was thelargest monthly total in the site’s 85-year history. Between January andMay, total production was up byabout one third over the same peri-od of 2009.

Between Krefeld-Uerdingen,Jinshan and Porto Feliz in Brazil,Lanxess has some 350,000tonnes/year capacity of Bayferrox. Itis continuing to implement processand logistical optimisation, efficien-cy increases and plant expansions toincrease capacity as demand for pre-mium iron oxide pigments growsworld-wide, investing a total ofabout €20 million at all three sitesthis year.

Lanxess optimises yellow iron oxide pigments

Bayferros production at Krefeld-Uerdingen has hit record levels


News



SINGAPORE-FINLAND

Kemira has begun a two-year R&Dcooperation with the SingaporeMembrane Technology Centre atNanyang Technological University(NTU). The stated aim of this is “todesign a more efficient water pro-duction process with a higherrecovery rate, lower energy con-sumption and less waste volume”,in support of Kemira’s own Centreof Water Efficiency Excellence inFinland, which was launched inMarch.

“Kemira will develop togetherwith NTU an improved used waterreclamation process with higherrecovery rates. By contributing ourvast experience in water treatmentchemistry, we aim to work withNTU to produce more clean andusable water with less energy andwaste,” said Kaj Jansson, vice presi-dent of R&D and technology.

Like many countries in South-East Asia, Singapore depends onreclaimed and desalinated watersources. In 2006, the governmentidentified the environment andwater industry as a strategic keygrowth area and committed €189million to develop Singapore as a‘global hydrohub’. Now some 70water companies operate regionalheadquarters, manufacturing andR&D activities here.

Earlier, Kemira had agreed to sellits global fluorescent whiteningagents (FWAs) business, which itacquired as part of Lanxess’s formerpaper chemicals interests, to Catec, aGerman firm with financial backingfrom Fengler Beteiligungs. The dealcovers production plant inLeverkusen, the global sales networkand the associated support functions.

Petri Helsky, head of the Paper seg-ment at Kemira, said that the compa-ny “is focusing according to its strate-

gy on products and services thatenhance the water quality and quanti-ty management in the water-intensiveindustries, such as pulp and paper”.Exiting from FWAs is in line with this.

About 100 people will transferwhen the agreement closes, which

is expected to be in August, andnegotiations are in progress withthe Works Council. Kemira addedthat this transaction will not haveany significant impact on its finan-cial figures and it is not disclosingthe transaction price.

Membranes in, white out for Kemira

Singapore is emerging as a ‘global hydrohub’

UK-GERMANY-US

The growing demand for new mate-rials for high-technology batteries iscreating major interest among spe-ciality chemicals firms. Within thepast month, Germany’s Süd-Chemie,Thomas Swan of the UK andChemetall Foote in the US have allmade important announcements inthe field.

Süd-Chemie is investing about€60 million to build a new facilityfor the production of lithium ironphosphate (LFP), a high perform-ance energy storage material used inbatteries for electric vehicle drivesand other applications. This willcome onstream in 2012 at the firm’sCanadian subsidiary, PhostechLithium, in Candiac, Quebec.

Capacity will be 2,500 tonnes/year, on top of 300 tonnes/year ofexisting capacity at the Moosburgsite in Germany - enough for 50,000all-electric or up to 500,000 hybridelectric vehicles. The new site willproduce LFP via a proprietary wetchemistry process.

Süd-Chemie’s Life Power-brandLFP is said to combine high energy

density with superior safety, a longservice life, a favourable manufactur-ing cost profile and excellent cyclestability. The company already sup-plies LFP for power tools, starter bat-teries and electric scooters.

Meanwhile, under a new long-termagreement, Thomas Swan will supplycarbon nanotubes, first in R&D quan-tities and ultimately in commercialvolumes to US-based battery technol-ogy development company VendumBatteries, on an exclusive basis “at apreferential price”.

Vendum has a pending patent onits eponymous carbon nanotube-and cellulose-based, lightweight andvery thin battery. This, it says, con-tains none of the toxic elementsused in conventional batteries and isentirely biodegradable.

The firm plans to develop thisfrom its current low power capacityto meet growing demand for greenerproducts in the €50 billion/year mar-ket for personal batteries in applica-tions like mobile phones, iPods andhuman implants.

This follows shortly after the com-missioning of Thomas Swan’s single-wall carbon nanotube (SWNT) plantat its Consett site. This began com-mercial production in late May and asecond, identical plant will be com-pleted by the end of the year. Eachwill be able to produce 50 kg/monthof Elicarb brand SWNTs.

Finally, Rockwood Holdings’sChemetall Foote subsidiary hasbegun expansion of its lithium pro-duction operation in Silver Peak,Nevada, with a view to expandingand upgrading the production oflithium materials for advanced trans-portation batteries. Silver Peak is theonly active lithium mine in the USand the project is part-funded by a€22.6 million grant from the USDepartment of Energy.

The investment will include a well-drilling programme to double lithiumcarbonate capacity. In addition,Chemetall Foote will put in a geother-mal power plant to make the opera-tion self-sufficient in power. To date,some 20 jobs have been created bythe expansion and 50 more peoplewill be employed at the peak of con-struction between 2011 and 2012.

Three power up in batteries


ITALY-UK-FRANCE

The slimming down of Big Pharmahas continued apace, with bothGlaxoSmithKline (GSK) and Sanofi-Aventis selling sites in the past month,to Aptuit and Covance respectively.Further changes may be in thepipeline after Merck & Co. announcedthat it would sell or close eight manu-facturing sites and eight R&D sitesworldwide.

Aptuit, a global pharmaceuticalservices company headquarted in theUS, has reached an agreement toacquire GSK’s Medicines ResearchCentre in Verona, Italy. No time-frameor financial terms were disclosed. GSKis also rumoured to be selling its GSKChemical Development site inTonbridge, UK, to Cherokee Pharma -ceuticals of the US.

This will bring Aptuit 500 new staff,who will continue to supply GSK withR&D services from the facilities. TimTyson, chairman and CEO of Aptuit,described the transaction “an exampleof the developing new model of out-sourced R&D collaborations”.

This brings to 19 the total numberof locations of Aptuit, which is ownedby private equity firm Welsh, Carson,Anderson & Stowe and now offersdevelopment and manufacturing serv-ices to some 800 pharmaceuticals andbiotechnology companies. It will com-bine its existing capabilities with theVerona site’s expertise in drug discov-ery, lead optimisation, API develop-ment and manufacturing and pre-clin-ical and clinical drug development.

The deal was said to have financialsupport from the Italian governmentand the approval of the local unions.GSK had decided in February to stopall discovery research in certain neu-rosciences areas such as pain anddepression, which meant that its needfor the Verona facility was greatlyreduced.

Philadelphia-based Cherokee,which is widely believed to be on theverge of acquiring GSK’s Tonbridgesite, is owned by PRWT Services andmanages the former Merck site atRiverside, Pennsylvania, which itacquired in January 2008. This site,which employs 390, now offers con-tract manufacturing services for APIsas well as having a five-year continu-ing supply agreement with Merck.

Cherokee has been actively lookingfor more sites to buy, so taking on

Tonbridge would not come as a greatsurprise. Moreover, the company pres-ident is John Elliot, who had previ-ously sold GSK’s site at Montrose inScotland to Akzo Nobel Diosynth in2002, when he was senior vice-presi-dent of GSK Primary Manufacturing.

Separately, Sanofi-Aventis hasrevealed plans to sell two R&D facili-ties in Porcheville, France, andAlnwick, UK, to the multinationalgiant CRO Covance under a non-binding memorandum. Terms werenot disclosed. This came a year afterthe company said that it would sellsome of its sites. Talks reportedlybegan in late 2009.

Whether the two sites would con-tinue to supply Sanofi-Aventis under along term contract, as is often the casein such acquisitions, is still unclear.Both are focused on pre-clinical trials.Porcheville, which dates back to 1976,works mainly in chemistry and toxi-cology, while Alnwick is focused ondrug safety assessment.

This transaction would result insome 330 employees transferringwhen the deal closes, which is expect-ed to be by the end of the year.Covance had previously acquired EliLilly’s pre-clinical research facility inGreenfield, Illinois, in August 2008, inwhat is widely seen as the model forsuch transactions between BigPharma and CROs.

Merck, meanwhile, has announcedthat it will fully or partially close orsell eight manufacturing plants andeight R&D laboratories as it seeks toshrink the R&D and manufacturingbase following the completion of themega-merger with Schering-Plough inNovember 2009.

This gave Merck a total of 91 facili-ties. Coupled with previous closures,this will now come down to 77,including 29 animal health facilitieswhich are not affected. In this field,Merck is merging its IntervetSchering-Plough subsidiary withSanofi-Aventis’s Merial.

The cuts are expected to reduce theworkforce by 15%, while saving costsof €2.1-2.4 billion/year. The first phas-es of the programme, however, willcost Merck some €2.8-3.4 billion. Thecompany is focusing on seven thera-peutic areas of: cardiovascular disease;diabetes and obesity; infectious dis-ease; oncology; neuroscience andophthalmology; respiratory andimmunology; and, women’s healthand endocrine diseases.

On the chopping board, therefore,are manufacturing locations atAzcapotzalco and Coyoacan, Mexico,Santo Amaro, Brazil, Mirador,Argentina, chemical production at theexisting Merck site in Singapore(though pharmaceutical manufactur-ing will continue there and at theSchering-Plough site), Comazzo, Italy,Cacem, Portugal and Miami Lakes.Mirador and Miami Lakes are specifi-cally earmarked for sale.

In addition, relatively small R&Dsites at Montreal, Canada, Oss,Schaijk and the Nobilon facility atBoxmeer in the Netherlands,Odense, Denmark, Waltrop inGermany, Newhouse in Scotland andCambridge, Massachusetts, will allgo. This will reduce the number ofR&D labs from 24 to 16, thoughMerck will retain clinical and regula-tory affairs expertise in all majorregions.

News



In BriefJM buys X-ZymeJohnson Matthey has acquired X-Zyme of Düsseldorf, which devel-ops and makes enzymes for themanufacture of chiral alcohols, par-ticularly oxidoreductases, chiraldiols and chiral amines for pharma-ceuticals and fine chemicals. This, itsaid, will complement its Catalysis& Chiral Technologies (CCT) busi-ness unit’s expertise in chemocatal-ysis based on chiral ligands forasymmetric hydrogenation, plat-inum group metal-based andSponge Nickel catalysts, plus relat-ed services.

AkzoNobel sharpens focusAkzoNobel has agreed to sellNational Starch, which makes foodingredients and speciality starchesfor industrial use, to Corn ProductsInternational for €1,030 million.The deal should close at the end ofQ3, subject to regulatory approval.CEO Hans Wijers said that this“marks the strong focus on our corebusiness and confirms AkzoNobel’stransformation into the world’slargest global coatings and speciali-ty chemicals company”.

ISP to work with VivimedISP has concluded a manufacturingalliance with cosmetic active ingre-dients maker Vivimed Labs ofHyderabad, India. The two will“work together to optimise manu-facturing assets dedicated to UVabsorbers”, jointly marketing cer-tain UVA and UVB protection prod-ucts for consumer sprays andlotions via its global sales, market-ing and technical service teams,with ISP adding Vivimed’s productsto its own Escalol brand portfoliofrom October.

Squeeze out agreedAltana shareholders agreed at theirAGM in June to transfer theremaining shares to the company’smain shareholder SKion, a vehicleby which owner Susanne Klatten istaking the company private after 33years on the German stockexchange. SKion already owns95.04% of the shares. Once this‘squeeze out’ has been entered intothe Commercial Register, theremaining shares will be transferredto SKion in return for a cash com-pensation of €15.01/share.

Aptuit, Covance buy R&D sites

GSK, like most Big Pharma companies, is scaling back manufacturing


In the May edition of SCM, a figurein the article by GAB Consultingincorrectly had ‘No Safe Use’ ratherthan ‘Safe Use’ in part of a flow chartshowing the steps to the authorisa-tion of a biocidal product under theBiocidal Products Directive due to aproduction error. The correct figure isshown here (below).

In addition, in the March edition,the structure of Smopex 101 was

shown incorrectly in the article byJohnson Matthey; it contains SO3,not SO2. The figure above shows thecorrect structure.

BP producerinventory

PreliminaryR.A.

Further mitigation/refinement

Risk mitigation/refinement

Dossierpreparation

Safe use

Safe use

CA evaluation Submission

BP Authorisation

No safe use

No safe use

SO3'H+

Smopex-101Styrene sulphonic acid grafted

polyolefin fibre

Corrections

News



CHINA-FRANCE

Rhodia, which is a major player insurfactants via its Novecare ‘enter-prise’ is to acquire an 87.5% stake inFeixiang Chemicals (Zhangjiagang)(ZJG), China’s largest producer ofamines and surfactants. It believesthat the €387 million deal, which isexpected to close in 2H 2010, sub-ject to approval from the Chineseauthorities, will be accretive to earn-ings from the first year.

Chairman and CEO Jean-PierreClamadieu said: “This acquisition isa key step in the implementation ofour profitable growth strategy.Through the integration of ZJG, wesignificantly strengthen our leader-ship positions in the surfactant busi-ness, while enhancing our footprintin the world’s fastest growingregion.” Once this is complete,around one third of Rhodia’s saleswill be in Asia.

Based in the city of Zhangjiagang,110 kilometres from Shanghai inJiangsu province, ZJG employs

about 650 people. It has been enjoy-ing 20%/year growth in recent years,as well as increasing profitability,selling a complete range of fattyamines and speciality amines.

Via ZJG, Rhodia will be able tointegrate speciality amine technolo-gies into Novecare’s business portfo-lio, adding capacity to its ownexpertise in formulation and end-market applications in speciality sur-factants for home and personal care,

agrochemicals, oilfield and generalindustrial applications. It plans todouble the size of the acquired busi-ness within the next five years.

Separately, Rhodia has agreed tosupport the Chair of Pine Chemistry& Natural Resources at the newUniversity of Bordeaux Foundation.The stated aim is to expand the roleof plant-based raw materials in thechemical industry, notably pine treeproducts, which are superabundant

in France and which Rhodia alreadyuses in surfactants and ingredientsfor paints and varnishes.

Rhodia is present in the Bordeauxregion through its Laboratory of theFuture, a joint research centre withthe CNRS and the University ofBordeaux. Via this new partnership,it will work with the university’s lab-oratories on new products. 10% ofits raw materials are already plant-based.

Rhodia in Chinese surfactant maker buy

Acquiring ZJG will strengthen Rhodia in personal care, agrochemical and oilfield applications

US

Chemtura and 26 of its US affiliateshave filed a Joint Plan ofReorganisation and a DisclosureStatement with the US BankruptcyCourt for the Southern District ofNew York, which is expected to con-sider approval of the statement short-ly. This could enable the company toemerge from Chapter 11 bankruptcyprotection within a few months

Chairman, president and CEOCraig Rogerson described filing theplan as “a significant milestone in theChapter 11 process, demonstratingChemtura’s progress toward emergingas a stronger, leaner, global enterprise.It is a testament to the outstandingprogress we have made in restructur-ing our finances and operations,” headded.

The plan, as described recently, isfor all worldwide operations ofChemtura and its subsidiaries to con-tinue in business. Some ‘treatment’ isenvisaged for funded debt obliga-tions, trade claims and litigationclaims, including those related to

diacetyl, and for all creditors to bepaid in cash or common stock of areorganised and publicly traded com-pany at or near the full value of theirclaims.

This is supported by Chemtura’sofficial committee of unsecured credi-tors and an ad hoc committee ofbondholders. The company hadrevealed in late May that it was in theprocess of finalising agreements withboth on the subject. It will continue towork with the official committee onany concerns they may have about theplan, which, it said, “provides thepotential to satisfy all creditors’ claimsin full, as well as offering value toequity holders”.

The disclosure statement includes ahistorical profile of the company, adescription of proposed distributionsto creditors and equity holders, anddetails of the ‘new’ Chemtura, plusmany of the technical mattersrequired for the solicitation process,such as descriptions of who will be eli-gible to vote on the plan. Both docu-ments can be viewed online atwww.kccllc.net/chemtura.

Chemtura files Plan ofReorganisation


Shackles on innovationAgrochemical innovation is more necessary than ever, yet has never been more costly and difficultto do. We report from Informex USA 2010




Agrochemicals, crop production and global food supply:these were the themes of two breakfast meetings dur-ing Informex USA 2010, which took place in San

Francisco in February. With the almost simultaneous release ofa new study commissioned by the US and European trade asso-ciations on the R&D costs of new crop protection products, anumber of key issues were brought into sharp focus.

It was appropriate, said one speaker at Informex, Mary-AnnWarmerdam, director of the California Department ofPesticide Regulation, to be discussing such issues inCalifornia. This is not only the US’s number one farming state,accounting for 11% of all farm revenues, but it also has themost extensive pesticides regulatory regime in the US and pos-sibly in the world.

Session moderator Jay Vroom, president and CEO ofCropLife America, the US trade association, observed thatcrop protection is and will remain essential; indeed, “the wiseuse of scientific technology is the reason we can feed over 6 bil-

lion people and our only hope to feed 9 billion by 2050”. Plantscience technologies help farmers grow more food on less land,while crop protection prevents the loss of 40-80% the crop topests, weeds and diseases.

0

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According to a study commissioned byCropLife America and the EuropeanCrop Protection Association (ECPA),the costs associated with the discovery,development and registration of newcrop, pest and disease agentsincreased by 64.8% to €256 million(€189 million) between 1995 and2005-8. This is in large part because ofthe regulatory burden on the industry.

The report, which was carried outby consultants Phillips McDougall,looked at R&D costs among 14 agro-chemicals companies, including four ofthe ‘Big Six’ R&D-based players pro-ducers - Syngenta, Bayer CropScience,DuPont, Dow, BASF and Monsanto -and some generics producers. Theirtotal R&D costs in 2007 amounted to€1,701 million, or 6.7% of their agro-chemical sales.

Breaking costs down at each stageof the process showed clearly that theincrease has mainly come in the ‘D’phase of R&D, where costs haveincreased by 84.8% to $146 million,whereas the costs of the ‘R’ phase haveactually fallen since 2000 (Figure 2).The most significant rise of all came inthe costs of environmental chemistryand toxicology, which are 63.4% up to$67 million.

This, says Phil Newton of the ECPA,can be directly related to the regulato-ry environment, especially that inEurope. Changes that were made to

the Plant Protection Products Directive,91/414/EC, in 2009 but which are onlybeing implemented now have meant aswitch from risk-based to hazard-based assessment criteria, on top ofthe costs of registration effectivelyreducing the number of products onthe market from over 1,000 to nearer300, in most cases because the cost ofpre-registration was not deemedworthwhile.

“The key thing is that cost of a cred-ible risk-based assessment was increas-ing anyway because of product safetyand environmental effect issues, but ina legitimate way,” Newton says. “Now,it is going over the edge into a situa-tion where a product can be bannedoutright based on a hazard assessmentor effectively banned because ofunreasonable standards.”

No other chemical-based industryin Europe, adds Newton, is regulatedthis way. Cosmetics, for example, areregulated on explicitly risk-based crite-ria. And yet, pesticides are more need-ed than ever, not least because pests’life-spans are so short and a new formof immunity is found somewhereevery year.

Field trials have also become morecostly. This reflects not so much theeffects of regulation as the conse-quence of combinatorial chemistry andhigh-throughput screening generatingvast quantities of leads. The number of

compounds going into initial researchevery year is about 140,000, of whichone or two might make it to market.

Time pressures - it takes an averageof 9.8 years from first tests to productregistration - mean that it is no longerpossible to do all the necessary screen-ing of lead compounds before gettinginto research. Trials are increasinglytaking place during the developmentphase, so more has to be invested inproducts that will ultimately fail.

Agrochemical intermediates andactives were not covered per se in thereport, notes author Matthew Phillips.Broadly speaking, though, industrytrends for producers of intermediates

and actives have meant that the vol-umes are positive but the spread ofproducts has narrowed a lot and thistrend is expected to continue.

Overall, the ECPA argues that agro-chemical R&D in the EU is becomingincreasingly hard to justify, despite theurgent need for innovation to addressglobal mega-trends. The best thing theEU can do, it adds, “is to establish a sci-ence-based regulatory framework anddevelop policy grounded in the realityof agriculture and what R&D can actu-ally achieve”.

“There is still room to implementthis sensibly,” says Newton. “If it is not,the hammer could fall anywhere.”

Innovation is expensive

0

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Development67

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Toxicology Field trials

Chemistry Tox/Env Chemistry Biology Chemistry

Figure 2 - Discovery & development costs of new crop protection products,1995-2008

Source: Phillips McDougall

Figure 1 - Crop protectioncontribution to crop yields &remaining potential

Source: Syngenta, from E.-C. Oerke, JACS, 2006

Informex_breakfasts_p11-13_scm07_Informex 7/14/10 9:59 AM Page 11

12 Jully 2010 Speciality Chemicals Magazine



However, he added, the last two years have seen a majorchange in the way the mainstream media covers the issues,with the perception of a global food crisis arising out of highfood and commodity prices and increased growth of biofuels.Chemicals are often being mentioned negatively in thedebunking of the concept of ‘cheap food’.

“The industry needs to tell the story of how it feeds us,” con-cluded Vroom. His words were echoed by most of the otherspeakers, not least those from the world’s two largest agro-chemicals companies. Both of these detailed how global mega-trends are shaping the crop protection market and their com-panies’ strategies and actions within it.

Dr Johannes Lubosch, head of raw material procurement atBayer CropScience, highlighted four mega-trends in agricul-ture, all of which are combining to make food supply a globalchallenge. The company has identified these as the centralfocus of its R&D activities in crop protection, seed breeding andplant biotechnology:1. Growing world population, leading to increased food and

energy demand but also a falling amount of farmland percapita. From 1950, when the world had less than 3 billionpeople to feed, to 2050, when it will have 9 billion, arableland is expected to fall from 0.52 hectares/person to 0.18

2. Growing wealth, leading to increasing meat consumptionand thus increased need to grow animal feed

3. The need for alternative energy feedstocks, particularly bio-fuels and renewable energy, thus creating competition withfood, feed and fibre crops

4. Climate change and the consequent threat of yield lossesDavid Marlin, head of formulation and tolling for the NAFTA

region at Syngenta, and Domnic Dyer, chief executive of theUK’s Crop Protection Association, both added limited watersupplies to this list. Between 65% and 70% of the world’s freshwater is already used in agriculture and the challenge is to useif more effectively, they noted.

To meet food demand in 2030, according to Marlin, wemust either put under cultivation an area the size of India orincrease productivity from a static area. In fact, he and Dyeragain agreed, there is no such choice; the extra land simply isnot there. If anything, erosion, climate change and urbanisationwill reduce the land available for farming.

“We must grow more from less. The only sustainableapproach is to unlock the potential of plants through innova-tion,” Marlin said. The world is already doing this, of course. Totalagricultural production increased by over 125% between 1960and 1995, while total arable and permanent cropland barelyincreased by 10%, thanks to new crop protection products andtechnology advances in seeds, GM and enhanced breeding.

Innovation in crop protection is vital, Lubosch added. Today’syield without crop protection would be 48% lower but moreimportant still, through innovations and adequate use of cropprotection systems, it could be 72% higher. For some crops, asMarlin separately pointed out, the remaining potential is stillvast (Figure 1).

“We can safeguard and increase yields from a constant landarea by better resource management, including the targeteduse of crop protection, and increased yields through innovativetechnologies,” he said. “We will also need to expand productionin marginal areas via new crops with greater tolerance ofdrought and extreme temperatures, while also increasing thetolerance of plants to climactic variability.”

Bayer’s innovation focal points in agrochemicals, both foragricultural and non-crop applications are therefore:

• New active ingredients & modes of action

• Developing new products, combinations, formulations &application technologies

According to consultant Jan Ramakers of theJan Ramakers Fine Chemical ConsultingGroup, who was also speaking at theInformex breakfasts, agrochemicals accountfor 2.5% of a total world chemicals market of$2.5 trillion, with base chemicals accountingfor 43%, pharmaceuticals 28% and others27%.

This gives it a total value of $40-42 billionthis year, following a steady increase from $28billion in 2000 and particularly strong growthin the last two years. About 30% of the agro-chemicals market, he said, is still proprietary -that is, subject to IP protection and/or exclusiv-ity rights - 40% is made up of proprietary off-patent products, which are not subject to suchrights but which are only made by one com-pany, and 30% are true generics.

“This is a very concentrated industry,”Ramakers noted. “There has been a lot ofM&A activity in the last 20 years: the top sixoriginators have 73% of total sales and the topsix generics producers have a further 18%, sothe top 12 together have more than 90% ofthe market.”

Of the total $87.7 billion market for finechemicals in 2008, Ramakers estimates thatpharmaceutical intermediates accounted for63%. Agrochemical intermediates were a fur-ther 8%, the same as flavours and fragrances.Dyes accounted for 5%, the remaining 16%being split among many others (Figure 3).

This market has seen strong growth in thepast decade. It was worth a little under $60 bil-lion in 2000 and $77 billion in 2005. An obvi-ous difference between agrochemicals andfine chemicals is the lack of concentration inthe latter; the top ten producers of fine chem-icals are reckoned to have only 14% of themarket. Even in pharma, the figure is onlyabout 45%.

Fine chemicals, according to Ramakers, typ-ically add 25-40% of the value of the product.The rest (60-75%) derives from formulation,marketing and other things.

Looking at the development of the agro-chemical intermediates market since 2000,Ramakers observed that it had often stuttered,with years of low growth interspersed with

actual declines. From about $6.1 billion in2000, it had reached around $6.5 billion in2006, then saw two years of much strongergrowth to reach its current level of $7.1 billion.

(Another speaker in San Francisco, DavidFrabotta, editor of Farm ChemicalInternational, attributed the strong growth in2006-8 to an “explosion in companion chem-istry” that accompanied the mass uptake ofbiotechnology in farming, particularly for her-bicides. By 2008, he noted, 125 millionhectares of transgenic crops in 25 countries,with soybeans leading the way, ahead of corn,cotton and canola.)

With more muted forecast growth of 1-2%/year, the world agrochemical intermedi-ates market should reach $7.7-7.8 billion in2013, said Ramakers. Further market growthfor both agrochemicals and their intermediatesand active ingredients seems likely because ofthe global mega-trends: population growth;growing food demand; increases in biofuelcrops; and, higher food prices. In part becauseagrochemicals generate fewer new activeingredients, the generics sector is seeing - andwill continue to see - relatively fast growth.

There has also been a tendency for agro-chemical intermediate production to beswitched into converted plants, mostly cGMP,that were built in the - unfulfilled - expectationof ever-growing demand for pharmaceuticalintermediates. However, these are rarely wellsuited to agrochemical intermediate produc-tion, for reasons of cost, regulatory issues andthe risk of cross-contamination.

“Because of this and the increasing marketshare of Asian producers, a lot of agrochem-ical intermediate production capacity hasbeen taken out of the market,” Ramakerssaid. “Now there are relatively few Westernproducers left”. KemFine, Albemarle, BASF,Saltigo, Lonza and DSM are among themost important.

There are three areas of opportunity for pro-ducers of agrochemical intermediates,Ramakers concluded: the growth of genericand proprietary off-patent products, outsourc-ing opportunities from the ‘Big Six’ and thegrowth of older established products.

Intermediate action

Figure 3 - Fine chemicals market by application, 2008

Sources: Jan Ramakers Fine Chemical Consulting Group





• Plant health (stress tolerance, yield increase & food quality)

• New approaches in biological crop protection & diagnos-ticsThese are all built on the major technology platforms of

chemistry, biochemistry and biology, genomics and bioinfor-matics, high-throughput screening and combinatorial chem-istry. The company, Lubosch added, plans to increase its R&Dspend by 16% from €649 million in 2008 to about €750million in 2016.

Of this, crop protection, one of Bayer CropScience’s threepillars alongside environmental science and bioscience, willaccount for about €500 million. Seeds and biotechnology willtake a further €200 million, environmental science the rest,but they will certainly not be replacing crop protection inBayer’s armoury.

“We have a strong commitment to chemistry,” Luboschcommented. Indeed, the company has launched 23 newactive ingredients since 2000. Sales of new active ingredientsincreased by 31% from €1,384 million in fiscal 2007 to€1,808 million in 2008.

Meanwhile, the share of new active substances grew from25.4% to 30.5%. Nine more herbicides, fungicides and insec-ticides with sales potential of up to €150 million/year each arecoming through the pipeline to 2012.

Marlin for his part highlighted a few emerging technologiesthat could bring plant potential to life, both increasing produc-tivity and/or reducing carbon emissions. Tropical sugar beet,corn amylase and the use of no-till production all offer extraor-dinary opportunities, he said. Syngenta itself is developing theModdus stress management chemistry, which can greatlyimprove water use efficiency.

“Films like ‘Food, Inc.’ have shown the downside. We need toshow the huge benefits chemistry and mechanisation havebrought in enabling us to feed a massively increased popula-tion,” said Dyer. “We proved Malthus wrong once, but we haveto do it all over again. The mega-trends are here to stay and thechallenge for the crop science industry is to develop the tech-nology that will help us to deal with them all.”

As ever, perception is a big part of the issue. Vroom showedsome results of surveys by Charlton Research in the US.Predictably, these showed strongly negative connotations by3:1 majority in peoples’ minds for ‘pesticides’, whereas ‘cropprotection’ scored a nearly 2:1 favourable response.

There was a strong general sense among those surveyed thatorganic is best. Even so, education on the issues showed that asolid majority of all groups surveyed, including the general USpublic, agricultural officials and health, science and environ-mental experts, could be swung behind the use of pesticides.

Dyer added that much of the regulation of pesticides inEurope in the last two years has been driven by NGOs’ demon-isation of them and of GM technology. This must be tackled,he said, because we could lose 30-40% of all crops withoutthem. Combined with the rising population, a continuationcould lead to a total catastrophe and the EU in general hasbeen slow to address the problem.

Seeing organic labelling as the solution, said Dyer, “is not justwrong, but very, very dangerous. Agrochemicals have a keyrole to play and companies need to know they will be able tomarket products before they spend €200 million over ten yearsto bring them to market. GM is not a replacement for agro-chemicals, they complement each other. Agrochemicals will bean important tool for years to come.”

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Simply the pestAre we on the verge of a new kind of chemistry in pest control? Elisabeth Jeffries reports

Strategies devised by worried farmers andpesticide producers to fight off aphids, pota-to scab and other pests plaguing them all

over the world were dealt a blow in 2008. Agroup of South German honey bee farmersreported a wave of bee deaths which they con-nected to the use of the neonicotinoid pesticideclothianidin.

The German government responded by ban-ning eight seed treatment products that usedneonicotinoids, a family of pesticides that was dis-covered in the 1970s and which are similar to thepesticidal compounds produced by the tobaccoplant. Wildlife news has hummed with reports ofbee disorders ever since.

This is not, of course, the first time that pesticidecompanies have come under attack. DDT, perhapsthe most vilified pesticide ever produced, wasbanned for agricultural use after similar rowserupted in the 1960s and 1970s.

Even if some of the more toxic pesticides havebeen outlawed, pests have in any case becomesmarter at fighting back at the many still in use. Anatural selection of increasingly smart productshas been the result as this war progresses onmany of the insect class, not to mention the nema-todes, fungi and other organisms that may ruinfarmers’ livelihoods.

Pesticides that target particular plants or attackparticular pests, potent pesticides that are onlyneeded in low quantities, pesticides that confusean insect and make it fly away - these are just afew of the products to have been developed sincethe scandals in North America nearly 50 yearsago caused by the indiscriminate spraying ofchemicals.

Synthetic pyrethroids were among the most bril-liant innovations in the field in the 1960s and 1970s,evolving in the laboratories of the pioneer chemistMichael Elliott at Rothamsted Research in the UK.His inventions showed that it was possible torespond to public concern by creating new insecti-cides that can be less harmful to the environment.

Elliott identified the most active components ofpyrethrum extract, a natural product found in thepyrethrum plant, Tanacetum cinerariifolium, amember of the daisy family which has insecticidalproperties, and he started to synthesise analogues.He and his team developed several sets of com-pounds which would revolutionise pesticide devel-opment in the 1980s and which still account forone third of the global insecticides market.

Having synthesised approximately 1,500 chem-icals based on pyrethrin, Elliott invented five mar-ket leaders in pesticide sales. Some, such asdeltamethrin, are still at the front of insect controltoday.

Not the least of his achievements was to syn-thesise a relatively small number of chemicals, as

1,500 is much less than the number of com-pounds usually generated in laboratories, whichruns into hundreds of thousands. This helped tospeed up the testing and development process.The products were also more benign than manypredecessors.

“Modern pyrethroids are much safer againstbeneficial organisms that might eat the pests,”comments Dr Tony Hooper, a biological chemistat Rothamsted Research. By contrast, some of theearlier pesticides, such as lindane, were eventuallyclassified as persistent organic pollutants that havea more widespread harmful effect.

The major pesticide types available whenpyrethroids were first launched includedorganophosphates which, though harmful to ver-tebrates, degrade relatively quickly,organocholorines such as DDT, neonicotinoidsand carbamates, which were first used broadly inthe 1960s.

Biopesticides, in which bacterial diseases controlorganisms harmful to crops, were also in exis-tence. These, like synthetic pheromones, whichare used to alter insect behaviour, have beenrevived in recent years and are used more fre-quently.

So it is fair to say that no major revolutionaryproducts have been launched on a large scalesince the 1980s. Professor John Lucas, head of

plant pathology and microbiology at RothamstedResearch, acknowledges: “There have been incre-mental improvements but not a new paradigmshift.”

That said, one potentially significant innovationmay have emerged. Dr Peter Lümmen, a bio-chemist at Bayer CropScience in Germany, arguesthat a new product, flubendiamide, only discov-ered five years ago by researchers from NihonNohyaku in Japan, could yield a whole class ofnew insecticides. It was first approved for use inthe US in 2008.

“We can justifiably say that the phthalic aciddiamides, to which flubendiamide belongs, haveblockbuster potential,” Lümmen claims.

Bayer CropScience indicates that the innovativecharacter of flubendiamide lies in its ability to tar-get a molecule found in insects without creatingmajor damage elsewhere. It could be used to killHeliothis virescens, the tobacco budworm that eatsfruit, vegetables and other plants and eventuallyturns into a moth, and is also generally a potentialinsecticide against lepidoptera.

Unlike other pesticides, flubendiamide aims atthe muscles rather than directly at the nervoussystem; this, too, is an innovative feature. Themembrane-bound molecule targeted by the sub-stance, known as the ryanodine receptor, plays apart in muscle contraction and calcium concentra-tion in insect muscles and has already been thesubject of chemical trials for years.

These, however, failed due to the toxicity of thechemicals used in relation other organisms too.The flubendiamide innovation relates to the factthat it targets a previously undiscovered part ofthe ryanodine receptor.

Ryanodine receptors in humans and in othervertebrates do not react in the same way toflubendiamide, according to Bayer CropScience,which has stated that it “wants to take advantageof these structural variations in the ryanodinereceptors to develop other insecticides based onphthalic acid diamide in the future.” These couldact on other insect pests.

Synthetic pheromones have made a fair contri-bution to pesticide development. Shin-EstuChemical of Japan has been a significant player inthis field, developing in 2006, for example, syn-thetic compounds of dodecyl acetate, a sexpheromone in the moth Tecia (Scrobipalpopsis)solanivora, which attacks potatoes in SouthAmerica.

Placed in a dispenser, the compound disruptsmating behaviour by interfering with communica-tion between males and females, camouflagingthe female signal and possibly reducing maleresponsiveness through sensory imbalance. Thisof course prevents the moth from reproducing ata normal pace.

Neonicotinoids were originally synthesised fromtobacco plants

Jeffries_p14-15_scm07_Jeffries 7/14/10 10:00 AM Page 14




Farms that prefer integrated pest managementhave often altered mating behaviour using syn-thetic pheromones, seeing it as a more benignway of controlling plant pests. Curiously, theyhave not been the most widely used control toolin agriculture.

In Europe, pheromones’ more marginal rolemay be about to change as Directive2009/128/EC on the sustainable use of pesticidescomes into force. This establishes a framework toachieve a sustainable use of pesticides by reduc-ing the risks and impacts of pesticide use onhuman health and the environment and promot-ing the use of integrated pest management andalternative approaches or techniques, includingnon-chemical alternatives to pesticides.

EU Member States are required to draw upaction plans to cut the risks to humans and theenvironment and to encourage integrated pestmanagement by 2012. So some pesticide produc-ers’ efforts to come up with new products may bethwarted. Not only do insects battle them byevolving new modes of resistance but Europeanauthorities are imposing a risk-based approach.“It’s a huge step forward in integrated pest man-agement in the UK,” remarks Nick Mole, a cam-paigner at the Pesticides Action Network, anNGO.

Concerns about the impacts of chemical pesti-cides are, perhaps, one of the factors affecting sci-entists’ attention to other methods for controlling

or managing pests. But Lucas says that one of themost important areas of research at the moment isto work out how pests develop resistance to exist-ing chemistry.

“The stewardship of current chemicals so theydon’t lose their effectiveness is the ‘now’ issue,” hecomments, adding that this problem is “a movinggoalpost”. Understanding the evolution of resist-ance and the genes responsible can then helpthem design molecules that get around it.

In the longer term, researchers are likely to usegenomics more and more to understand whysome insects are damaging to crops in the first

place and possibly to subsequently develop newchemicals. They can already, for instance, interro-gate the genome of aphids, which was firstsequenced in May 2010.

“Identifying the genes involved that made thema problem means that you can identify new tar-gets for intervention,” explains Lucas. Scientistscan devise new chemicals that interfere with a keyenzyme by designing a molecule that prevents atoxin from being synthesised. Nevertheless, theincreasingly strict regulatory limits placed on pes-ticide chemical development mean that this is achallenging and long term option.

However, genomics could be of use in helpingmanage pests by improving insights into theirbehaviour. Lucas points out that scientists are nowsequencing genomes in an afternoon - a hugestep from the major endeavours of the earlier partof the last decade.

“This gives us a hugely powerful compensatingresource, allowing us to compare different strainsand variants,” he explains. This could help toimprove intelligence relating to the whereaboutsand spread of a particular virus, for example.

“Extrapolating ten or twenty years ahead, wemight have smart biosensors and more rapid com-munications, but whether we manage using dif-ferent methods is another matter.” In the meantime, it is likely that major chemical innovationsfrom crop protection companies will become evenrarer.

Michael Elliott was the pioneer of pyrethrininsecticides from the pyrethrum

Jeffries_p14-15_scm07_Jeffries 7/14/10 10:00 AM Page 15




More from less inagrochemicalsDr Susan Brench and Dr Chris Rainford review how Pentagon Chemicals streamlines the introduction of new agrochemical products and optimise the performance of its existing processes

With the global population estimated to grow fromthe current 6 billion to around 9 billion by 2050,there has never been a greater need for increased

crop productivity to use the limited natural resources avail-able fully. One of the key enablers for this is the targeted useof a combination of herbicides, insecticides and fungicides toensure that the maximum yield is derived from each plant-ing. This philosophy - of getting more from less - is one thatPentagon Chemicals, as a supplier of active agrochemicalingredients and intermediates, has incorporated into its waysof working.

Pentagon’s fine chemicals operations at Halebank, UKwere purchased in December 2003 as part of a strategy tomix organic growth with the acquisition of complementarytechnologies and access to new markets. The site broughtwith it a long history of new product development in the lifesciences, adding bromination, chlorination, cyanation, phos-genation and sodium dispersion chemistries to the existingcore technologies of maleic anhydride derivatives andGrignard reagents.

In addition to widening the available technology toolbox,the integration of Halebank with the existing site atWorkington enabled teams from the two businesses to iden-tify and select individual best working practices with a view toestablishing a fully integrated programme of continuousimprovement for existing manufacturing processes, as well asnew product introductions.

Products & process developmentThe first step was to ensure that all employees across the siteswere fully engaged. At the heart of this objective was theconcept of the product team - a multi-disciplinary groupformed from representatives from all departments chargedwith ensuring the delivery of each customer’s expectations, inparticular a safe and sustainable operating environment, aswell as the development and production of the right productsat the right time and to the desired quality within the costboundaries agreed.

Productteams

Everyone knowskey customer

Continuous improvement throughtotal employee engagement

Visible safetyculture

Sustainabledevelopment

Visible costreduction plan

Right firsttime %

On timein full %

Scheduleadherence %

Figure 1 - Product team concept at Pentagon

For the fine chemicals business, the focus on productivityimprovements yielded immediate benefits with increasedoutput, higher yield and reduced waste achieved on manykey products. When the concept was expanded to includecustomers in the teams in order to provide greater integra-tion of objectives and transparency of progress, even furtheradvances in process development were realised.

At the core of each product team is a member from thePentagon technology group, who is tasked with employing aconsistent methodology to help determine the most effectivemethod of delivering improvements.

The process chosen to advance the understanding of thechemistry uses a Six Sigma approach to help define keyproduct and process outputs, identify the main drivers nec-essary in achieving these objectives, analysing their impacton performance before finally optimising them and ensuringsuccessful incorporation into the manufacturing procedures.This (Figure 2) employs the five-step methodology of define,measure, analyse, improve, control, as discussed below.

Five stepsRecently, Pentagon developed a two-stage process to pro-duce a novel agrochemical intermediate using its proprietarysodium dispersion technology, a unique method of safelygenerating 5-10 µm particles of highly reactive sodium toproduce an alkoxide moiety which could then be coupled toa halogenated substrate, as shown in Figure 3.

As in all highly regulated markets, product quality is ofvital importance to ensuring a successful outcome, not onlyfor us but for our customers as well. In this instance, theproduct team’s close collaboration with the customer enabled

Sodium dispersion is a key capability of the Halebank site

Pentagon_p16-17_scm07_Pentagon 7/14/10 10:00 AM Page 16




a detailed product specification to be created and its param-eters, including the identity and maximum limits of all criticalimpurities, to be set.

With a clear timetable agreed for development work andtrial manufacture, Pentagon’s technologists considered whichfactors would potentially determine the formation of theimpurities and used the methodology to design a series ofexperiments that enabled the maximum amount of informa-tion to be extracted from a minimum set of experiments.

The potential critical process parameters were identified bythe design team as the stoichiometry of reactants A and B,concentration, temperature and the feed rate of reactant C.In order to study each of the factors, a two-level factorialexperiment was designed. This resulted in a total of only 11experiments being carried out. Since each experiment tookover two days to complete, significant savings were made intime and resource when set against a full factorial study con-sisting of 32 experiments.

The results of the experimental design were analysedusing JMP software and the key controlling factor was iden-tified as reaction temperature. In this instance, indicationswere that lower temperatures favoured reduced levels of thecritical impurities.

Next, a targeted set of experiments were run at the lowertemperature setting to demonstrate that the process wascapable of producing material with the required impurityprofile (the CpK was 12, well above the target of ≥1.3). Thisgave us and our customer the confidence to move forward tomain plant manufacture without the need for intermediatepilot plant trials - a crucial factor in meeting the customer’sobjectives.

Using the information obtained from the laboratory work,the team then ensured that all the necessary controls were inplace for a successful scale-up. In this case arrangementswere made for a clearly documented manufacturing proce-dure to be produced, as well as provision for additional train-ing and support to the operations teams running the process.

R OH + Na R ONa + 1/2 Na

(a) (b)

R ONa +

(c)

R' X RO

R'+ NaX

Figure 3 - Reactive alkoxide via sodium dispersion

Greater automation of the plant was also introduced toensure that the process remained within the identified oper-ating parameters. The trial successfully produced material ata larger scale than all other sources and analysis of resultsfrom the production batches clearly demonstrated that theprocess was robust with respect to the key impurities.

ConclusionPentagon has found that the product team concept to be anexcellent platform for providing teams with the necessaryfocus and cross functional co-operation to deliver high per-formance in improving existing processes, as well as intro-ducing new products. This framework can be furtherenhanced by closer ties with customers in order to providegreater understanding of their needs.

Clearly defined project outputs and consistent use ofprocess improvement methodology then makes possiblemore efficient use of development resources, shorter cycletime from laboratory to plant, greater confidence in laborato-ry data and scale-up from laboratory to plant without theneed for a pilot plant stage.

For more information please contact:Dr Christopher RainfordPentagon ChemicalsLower RoadHalebankWidnes WA8 8NSUKE-mail: [email protected]: www.pentagonchemicals.co.uk

Define

Customer needs

Quality

Safety

Material usage

Throughput

Experimental design

Controlling factors

Tolerance levels

Fractionate

Measure

Statistical analysis

Significant factors

Predict effects

Optimise

Analyse

Verify optimumconditions

Robust process

Measure processcapability

Improve

Implement process

Training

Manufacturingprocedure

Software/hardwarecontrols

Control

Figure 2 - Six Sigma process improvement methodology

Halebank added phosgenation to Pentagon’s toolbox

Pentagon_p16-17_scm07_Pentagon 7/14/10 10:00 AM Page 17



So long, solvents

Stephen Coulson says that hehas yet to find a material thathe cannot put an invisible

water-repellent coating on usingplasma technology. It is not for wantof trying. After all, he is chief tech-nology officer at P2i, a UK companyspecialising in liquid-repellent nano-coatings.

Wood, leather, ceramics, glass,metal and paper can all be given anano-coat using P2i’s plasmaprocess, but these tests were just toshow how versatile the technologyis. The company is currently reapingrewards from a plasma process thatcan make shoes and boots instantlywaterproof by coating them with apolymer layer that is tens ofnanometres thick, invisible to thenaked eye.

Plasma is ionised gas which canbe created by passing a currentbetween two electrodes. The plasmaions ‘activate’ other molecules, suchas monomers, so they attach to thesurface that is to be coated, pavingthe way for polymer chains to growout and give a permanent coating.

Plasma technology has long beenused in packaging and to coat archi-tectural glass, microelectronics andcar components. The technology’smain selling point is that it requiresno solvents. This is a big deal for thetextiles industry, which currentlyconsumes huge volumes of water,often in parts of the world where it isscarce, but which has been slow toadopt the process.

The standard way to coat fabrics isto dip them in aqueous solutions ofchemicals which have been speciallyformulated for the particular type oftextile being coated. This is a suc-cessful process, but it has its draw-backs. “For some materials it is verydifficult to find the solution-basedprocess which will put the function-ality on the surface,” explainsCoulson.

Trying to apply water-based solu-tions to fabrics that are inherentlyhydrophobic is also tricky and oftenineffective. For plasma technology,by contrast, anything goes; it doesnot matter what the surface beingtreated is.

Utterly repellentFabrics that are inherentlyhydrophobic can be given a plasmatreatment to make them hydrophilicbefore they undergo chemical treat-ment, reducing the volume of waterneeded for the dyeing process andgiving a better colour fastness.

P2i focuses on making materialsliquid-repellent but is now looking atways to use plasma to give anti-microbial or fire-retardant nano-coatings. The company, which wasspun out of the UK Ministry ofDefence’s Defence Science &Technology Laboratory at PortonDown in 2004, having developed aplasma process to make liquid-repel-lent military apparel, is building onexisting anti-microbial knowledge,particularly in the area of quaternaryammonium salts, and has patentednew related monomers.

“What we were looking for wasthe highest level of repellency for awhole variety of liquids, not justwater: petrol, oils, lubricants, andalso chemical challenges that youmay see on the battlefield, such as

nerve agents or mustard gas - liq-uids with a substantial vapour pres-sure,” explains Coulson.

At the time, many in the plasmacommunity thought that it would bevery difficult to make the plasmaprocess - which operates in a lowvacuum - cost-effective, but Coulsonsays that P2i has done this and hassigned up brands such as Nike,Adidas, Hi-Tec and Ecco.

About 40% of its business is nowin textiles, with the rest in coatingsfor electronics. The company is cur-rently securing its next round offunding to take it through a “rapidgrowth patch”.

P2i’s successful entry into clothingand footwear is something of anexception in the plasma worldalthough it is far from alone in tar-geting the textiles industry. Belgiancompany Europlasma has madeplasma machines for coating textilesfor ten years but has had little inter-est from clothing textile manufactur-ers, despite major take-up by otherindustries, including medical devicemanufacturers.

“The clothing industry is very con-servative and difficult to penetrate,”says Peter Martens, product manag-er at Europlasma. “We have beentrying to get into the clothing busi-ness for the past two years but it isnot easy.”

Dirk Hegemann, from EMPA, aSwiss governmental research insti-tute which works closely with indus-try, can see where the industry’sreluctance to adopt plasma comesfrom. “The textiles industry hasinvested a lot in wet chemicalprocesses. A dry process - plasmatechnology - is new for them. Theywould not only need new equip-ment, they would also need newknow-how.”

The new equipment needed gen-erally incorporates a chamber to cre-ate the low vacuum required formost commercial plasma processes.This effectively puts a size restrainton the fabric that can be treated.

The low-pressure plasma process-es have the advantage of being triedand tested for many years by otherindustries. P2i, Europlasma andEMPA have all opted for these, quot-ing reliability and low-running costs.EMPA has developed low-vacuumplasma processes for an Austriantextile company called Grabher,which uses a ‘roll-to-roll plasmacoater’, and for Tersuisse, a Swisscompany that treats individual fibresusing plasma technology.

In principle, atmospheric pressureplasma technology would be far eas-ier to incorporate into productionlines - no vacuum is required and itpromises high throughput rates -but Hegemann is not aware of anycompanies using atmospheric pres-sure plasma to treat fabrics.

The technology is not that differ-ent to the corona (electrical dis-charge) treatment that the textilesindustry has been using for over 30years to activate textiles beforeapplying chemicals. Atmosphericplasma treatment simply takes theprocess further, activating and coat-ing a material in one step.

“In the early days a lot of peoplebelieved that you could only do plas-ma processing of fabrics at atmos-

Plasma technology is perfect for giving fabrics a water-repellent nano-coating, so why is the textilesindustry only just beginning to see its value, asks Emma Davies?

Sports shoes like the Magnum Boot Elite Force (above) and the Adidas Tour360 (opposite) are protected by P2i’s technology


Davies_p18-19_scm07_Davies 7/14/10 10:01 AM Page 18

dispersion, and you atomise it in aplasma atmosphere,” explains ArjanGiaya, vice-president of technologyat Triton.

The precursor and substrate areactivated simultaneously at atmos-pheric pressure and room tempera-ture so that the precursor polymeris-es and bonds to the activated sub-strate to create a coating with athickness of 10-200 nm. “You don’thave a heating source or a vacuumpump so the energy consumption isvery, very low,” says Giaya.

The drawback of the system, headmits, is that it needs to be done inan expensive inert gas atmosphereof, say, helium or argon. If thesystem were to operate in

air, the corre-spond-

ing high-temperature plasma woulddegrade the precursors. APPLDretains the original properties of theliquid precursor.

Triton has spoken to textile com-panies with a view to sub-licensingthe technology. Many are apprehen-sive about investing in new equip-ment in the current economic cli-mate but some are keen to adoptthe technology when they can affordto invest.

The company is out to identifyareas where ASSET is better thananything else available and it hashigh hopes for speciality textiles,especially high-end synthetic fibres.It currently offers a range of coat-

ings, including the standardhydrophilic, water-repel-

lent and oil-repellentones, but also

claims to be

able to mix polymers to give multi-functional surfaces.

“You can mix different active ingre-dients in the precursor stream anduse them at the same time or you cando a different treatment on each sideof the fabric,” explains Giaya. “So youcould have a fabric that is hydropho-bic on one side and hydrophilic onthe other or one that is both anti-microbial and water-repellent.”

Add to this work that Hegemannis doing at Empa on coating fibreswith silver, in which the metal issputtered by plasma, and there aresome interesting processes beingdeveloped. Metallised fibres couldbe used to incorporate electricalwiring into textiles, he says, bringingthe possibility of clothes that couldperhaps measure your pulse.

Such progress may be a leap toofar for the textiles industry but plas-

ma coating companies can per-haps be cautiously opti-

mistic about the textilesindustry adopting itstechnology. As water

usage becomes more ofan issue, plasma may become

the only choice.

Leather & textiles chemicals



pheric pressure level,” says Coulson.However, the techniques often havethe drawback of not being able totreat 3D items efficiently. “The func-tionality that you’re providing is stillat the fabric level and, in order toget it into the product, you wouldthen have to cut out shapes to forma garment.”

Breaking the mouldDow Corning has developed atmos-pheric plasma technology calledatmospheric pressure plasma liquiddeposition (APPLD), which it claimscan treat 3D objects. It has licensedthis to Triton Systems, a coatingscompany based in Massachusetts,which is combining APPLD with itsown chemistry and formulationexpertise in what it calls ASSET(advanced solutions in surface engi-neering technology).

What is unusual about APPLDis that it sprays tiny droplets of aliquid precursor such as amonomer into the plasma; otherprocesses use gas or vapour depo-sition. “Based on the functionalityyou want for your textile, youchoose a liquid or even a particle

Davies_p18-19_scm07_Davies 7/14/10 10:01 AM Page 19


Dr Michael Franken of Lanxess looks at the thinking behind the Aquaderm X-Shield technology


Demand for leather in light colours is increasing, espe-cially in the upholstery sector. From both aestheticand psychological points of view, car manufacturers

are tending to use more light brown, beige and even whiteleather seats, especially in the luxury car segment. Even fur-niture leather for dining room chairs and lounge suites isincreasingly being marketed in lighter colours.

Today, light-coloured upholstery leather has about a 20%share of the total upholstery market. Approximately 41.8 mil-lion m2 of furniture leather and 29.7 million m2 of automo-tive leather are produced in light colours.

Ecological & economic aspectsThe lifetime of a lounge suite upholstered with light-colouredleather depends very much on the anti-soiling and the clean-ability performance of the leather employed - and brightcolours are, of course, more sensitive by nature to soiling andstaining.

This fact is also very important from the environmentalpoint of view. Modern life cycle assessments of articles ofleather furniture evaluate more than the manufacturingprocess of the leather and subsequent furniture production.They also look at the lifetime and final disposal of the articleand these aspects are likely to play an even more importantrole in the future.

This highly complex topic can be put quite simply: if theworking lifetime of an article can be doubled, its environ-mental impact is reduced by 50%. Compared to the effortneeded to improve a manufacturing process in order toachieve a better life-cycle rating, efforts in development areoften much more efficient.

Since a positive environmental profile for an article is moreand more valued, from our point of view it is worthwhile toestablish and develop further best practice technologies interms of anti-soiling and cleanability. With light-colouredleather, this means that high performance chemicals andadditives are needed.

Such products are true speciality chemicals, which maynoticeably increase the cost of a finished formulation.However, if one weighs the additional performance versusthe additional cost, the consumer’s willingness to spend moremoney on such high quality products should not be under-estimated.

The market price of a high quality leather lounge suiteranges from approximately €3,000 up to about €10,000. Atypical SUV vehicle fitted out with leather costs approximate-ly between €2,000-8,000 more than a standard textile edi-tion. Comparing the additional cost of some €5-10 perlounge suite or car seat for a best possible anti-soiling andcleaning performance, the enhanced longevity of such arti-cles with the commercial value of those items, the cost can beconsidered of minor importance.

Today it is possible to produce leather with a long lastinganti-soiling and cleanability performance which remains or canbe kept clean over an extended period of time, thus maintain-ing its initial value. Promotional packages which include, forexample, warranties for the final consumer would compensatefor the additional cost of such articles and improve the imageof leather as a durable material substantially.

Best practice technology:Based on this economical and ecological assessment, Lanxesshas dedicated significant R&D resources in the field of anti-soiling and cleanability in recent years. New chemicals havebeen developed, formulations have been screened and opti-mised and test procedures have been established. The result-ing products and the application technology are marketedunder the brand Aquaderm X-Shield.

During these studies, it became clear that a perfect anti-soiling and cleanability performance is not just an additionalcriterion which can be achieved by simply adding certainchemicals into a top coat formulation. As described in the lit-erature, anti-soiling and anti staining performance must bedistinguished, because different contaminants have differentimpacts on the degree of damage they may cause onleather.1-3

Soiling is the constant and regular exposure of leather tocontaminants through daily use. The most common contam-inants are dust, carbon compounds, oils and dyestuffs fromtextiles. Staining means the accidental and occasional con-tamination of leather goods by, say, wine, coffee, lipstick,pens or a myriad of other substances, which can contributeto a significant loss in value for, or even destroy, preciousleather goods.

Because of this, Lanxess thought it important to developdifferent testing methods focusing on the required perform-ance characteristics of the respective leather articles. In thecase of staining, the contaminants are applied directly ontothe leather and wiped off after a certain residence time withcommon household cleaners, after which their cleaning effi-ciency is evaluated.

In the case of soiling, which is an important issue in theautomotive industry, standardised fabrics contaminated withdifferent pollutants are rubbed over the leather by means ofthe Martindale abrasion tester. The degree of colour changeis measure after 2,000 cycles, then the dirt is wiped off bymeans of common leather cleaners and the colour change ismeasured again.

During the development phase of the Aquaderm X-Shieldsystem, it became clear that such a wide variety of potentialcontaminants, along with an even bigger number of differentleather properties, requires individual anti-soiling systems. Ourgoal was to achieve the best possible spectrum of efficacy.

Although a ‘one-size-fits-all’ system does not exist, wefound that polymers with built-in tetrafluoroethene (TFE)


Eco & economical advantages of an

CH2

COO-

HN+R3

R1

CH2 aCH

XHN+R3

R2

CHb

CF3CF3 cCH

Y

CH2 dCH

Z

CH2 e

COO-

HN+R3

Pigmentdispersibility

Film formation/transparency

Anti-soiling/cleanability

Cross-linking/adhesion

Dispersionstability

- Functional groups: approximately 50% in total

- Built-in PTFE segments: approximately 50% in total

Figure 1 - Structure of newlinear TFE copolymer

Lanxess_p20-21_scm07_Lanxess 7/14/10 10:02 AM Page 20



units were the most suitable substances for such applications,as they have a performance profile which is very similar topolytetrafluoroethene (PTFE). This is essentially becausePTFE:

• Provides hydrophobic and oleophobic effects at the sametime

• Is thermostable at temperatures from -200°C to +260°C

• Is chemically inert and resistant to UV radiation

• Provides low friction and excellent release properties

• Has extremely low surface energyIn practice there are two ways of using this chemistry in

the leather field namely the so-called comb polymers or vialinear copolymers. Comb polymer-based products containingTFE side chains, such as Aquaderm X-Shield L, are used asan additive in special top coats and provide outstanding dirtrepellency and cleanability.

Analysis of leather finished with Aquaderm X-Shield L hasproved that neither perfluoroctyl sulphonic acid (PFOS) norperfluoroctanoic acid (PFOA), which both present environ-mental issues, is present. Nevertheless, there is a drawback tocomb polymers in that cross-linking is only partly possible,which limits the durability of such systems.

In the case of linear TFE-copolymers, such as Aquaderm X-Shield G and M2, the TFE groups are permanently built intothe polymer backbone. Combined with additional functionalgroups, such products offer a versatile application field to the

leather industry, adding durability to the excellent dirt repel-lency and cleanability of comb polymers.

In cooperation with Daikin, Lanxess has been able todevelop a water-based linear TFE copolymer for use inleather applications. Finishing systems based on this uniquechemistry can be pigmented and cross-linked with iso-cyanate, which leads to an excellent film formation. At thesame time, different gloss levels can be adjusted and suitablefeel agents can be added.

By these means a superior and long lasting anti-soilingresistance along with an outstanding cleanability perform-ance can be achieved. Figure 1 shows the linear polymerstructure of these systems.

ConclusionAquaderm X-Shield technology can provide leather articleswith outstanding performance in terms of anti-soiling andlong term cleanability, generally summarised under the term‘anti-soiling’. Depending on the requirements, formulationscan and must be customised for each individual purpose.

Specially developed high performance polymers based on flu-orocarbon are used in carefully balanced recipes provide anti-soiling performance without sacrificing other physical require-ments. The additional cost for this chemistry is not negligible, butit gives additional value to the consumer because it extends thelife of a high performance article.


es of anti-soiling leather protection

Organised by: In association with:

Offi cial media partner:

Contact the sales teamIndiaVijay RaghavanT: +91 (0) 22 2404 4472E: [email protected]

InternationalJohn LaneT: +44 (0) 1737 855 076E: [email protected]

www.chemspecindia.com

14-15 April 2011Hall 1Bombay Exhibition CentreNSE Goregaon (E)Mumbai | India

References:1. D. Tegtmeyer, T. Hassel, J.Reiners, S. Wildbrett & M.Franken, Leather, April 20092. D. Tegtmeyer, T. Hassel & M.Franken, Pro-Leder, December20083. J. Reiners, T. Hassel, R.Maier, S. Wildbrett, D.Tegtmeyer, M. Maeda, K.Imoto & A. Ueda JALCA, 2007,102(10), 322-336

For more information,please contactDr Michael FrankenHead of Leather FinishingLeather BULanxess AGE-mail: [email protected]:www.lanxess.com

Lanxess_p20-21_scm07_Lanxess 7/14/10 10:02 AM Page 21


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Dr Marco Arnold and Dr Cornelia Röger show how BASF develops key compounds for ever smallernode sizes*


Every microchip comprises a base layer of transistorswith several layers of wiring stacked above to connectthe transistors to each other and finally to the rest of

the computer (Figure 1a). These interconnects are todaybased upon copper and form a complex three-dimensionalnetwork of horizontal and vertical lines, called trenches andvias, with a total length of up to several kilometres.

The first copper-based microprocessor was manufacturedby IBM in 1997 using a completely new integration schemecalled the damascene process (Figure 1b). This had to bedeveloped because copper cannot be patterned by a reactiveion etching process.1

First, the formation of a barrier layer is required, prevent-ing the diffusion of copper into the dielectric material.Currently a Ta/TaN barrier is deposited via a physical vapourdeposition (PVD) process on a patterned dielectric layer.

The creation of a copper seed layer in the following stepprovides the whole wafer with a conductive surface, facilitat-ing the subsequent electrochemical deposition (ECD) of cop-per. Finally, a chemical mechanical planarisation (CMP)process is required to remove the excess copper layer as wellas the barrier layer from the top of the dielectric.

Since the semiconductor market demands ever faster chipswith higher power density and lower energy consumption,the race to fabricate devices with an increasing transistor den-sity continues.2 With each new chip generation (technologynode), not only the transistor dimensions but also the featuresizes of interconnects have to shrink.

Hand-in-hand with the decreasing feature size, therequirements to the electroplating chemicals used in thedamascene process are more and more challenging. Forexample, the feature openings of the 32 nm technologynode show a width of merely 20 nm after seed layer deposi-tion.

Role of additives The quality of copper interconnects determines the lifetimeand electrical performance of an integrated circuit. Thus, it isessential to avoid defects inside the copper lines. However, ifa substrate is electroplated without additives, voids areformed, due to a higher copper deposition rate at the wafersurface and feature opening compared to the feature bottom(Figure 2a).1

Perfectly filled structures can only be obtained if the cop-per deposition rate is high at the feature bottom and slow atits upper edges and at the top of the wafer. This superfillingprocess is realised by adding an accelerator and a suppressorto the plating bath.

Suppressors are polyalkylene glycol (PAG) polymers. Thesuppressing behaviour of PAGs can be explained by theiradsorption on the wafer surface. The adsorbed polymer filmacts as a physical barrier for copper ions, due to the forma-tion of PAG-Cu(I)-chloride complexes, and for acceleratormolecules, as well by limiting their access to the wafer sur-face. The most common accelerator used in industry is bis(3-sulphopropyl)-disulphide (SPS).

The superfill mechanism is caused by a sophisticated inter-play of additive transport and adsorption kinetics.3,4,5 Whena structured wafer is immersed into the plating bath, bothadditives are uniformly distributed in the solution (Figure 2b).

Due to its high adsorption rate, the polymeric suppressoradditive is rapidly consumed by film formation on the wafersurface. Since the wafer rotates in the plating solution, a con-stant convectional flow of electrolyte to the wafer surface is


Additives for copper electroplating

PVD Ta/TaN-barrierPVD Cu-seed

≈ 20 nm

ECD Cu

CMP

Connection toexternal circuitry

Interconnectlevel 5

Interconnectlevel 4

Interconnectlevel 3

Interconnectlevel 2

Interconnectlevel 1

Transistorlevel

Trench

Via

Cuinter-

connect

Cu Dielectric (low-k) Dielectric (SiO2) Ta/TaN-barrier W (contact)

Solder Transistor Silicon substrate

a b

a b c

d e f

Figure 1 - Microchip 2D cross-section, not to scale (a) & copper damascene process (b)

Figure 2 - Void formation via sub-conformal plating without additives (a) & adsorption &diffusion characteristics of accelerators (red) & suppressors (blue) during superfilling ofcopper (b-f)

BASF_p24-26_scm07_BASF 7/14/10 10:02 AM Page 24



induced, providing fresh supply of suppressors and resultingin the formation of a compact suppressor film on top of thewafer.

By contrast, the transport of additives into the feature is dif-fusion-controlled. Only a small fraction of the inner featuresurface is covered by the suppressor, caused by the low sup-pressor diffusion rate and a large surface to volume ratio(Figure 2c).

For this reason, the deposition rate at the feature bottom ismuch higher compared to the wafer surface. There, theaccelerator molecules are accumulated due their higher dif-fusion rate (Figure 2d).

The key function of the accelerator is to keep the featurebottom free of adsorbed suppressor and to maintain a local-ly high deposition rate (Figure 2e). Furthermore, during thesuperfill the accelerator deactivates the suppressor film at theupper walls of the feature by decomposing the PAG-Cu(I)-chloride complexes, resulting in a void-free filled feature(Figure 2f).

Suppressor synthesisUntil now, few structural variations of PAG derivatives havebeen published for use as suppressing agents. Establishedadditive formulation providers very often purchase commer-cially available PAGs that have not been developed specifi-cally for an electronic application. However, as the technolo-gy nodes decrease down to 32 nm and even smaller, thelikelihood of finding a commercial PAG derivative matchingthe challenging criteria to provide a fast and defect-freesuperfill becomes increasingly slim.

Since BASF has strong expertise in R&D into and in theproduction of PAG, it has successfully commercialised thisclass of polymers for many different applications, such aswashing and cleaning, as ingredients for cosmetic formula-tions, raw materials for polyurethanes and constructionchemicals, as well as agrochemical adjuvants. Recently, thecompany used its expertise in developing structure-propertyrelationships in the field of PAGs, designing tailor-made sup-pressor additives for current and future copper plating tech-nologies.

In addition to commercially available PAGs, an enormousstructural variety of these polymers is accessible. Synthesiscan be carried out by cationic, anionic or coordinative poly-merisation mechanisms, using ethylene oxide (EO) as a keymonomer. In addition, propylene oxide and higher alkyleneoxides serve as additional components to synthesise statisti-cal or block copolymers, while alkylene oxides carrying func-

tional groups as substituents allow further fine-tuning of thePAG’s properties.

Many different molecules can start the polymerisationreaction, i.e. alcohols or amines, but other nucleophilic com-pounds have also been employed. This further multiplies thestructural variety of PAGs (Figure 3). A broad range of suchPAG structures was synthesised to gain access to suppressorsshowing a huge spectrum of different physical and electro-chemical properties.

The handling of alkylene oxides, especially EOs, requiresspecial safety measures and well-trained technical staff. EOhas an extremely high ring tension, leading to a very highreactivity, for example with traces of nucleophilic and acidicresidues, and self-decomposition at elevated temperature,which can be catalysed even by traces of rust. Thus, handlingobviously has to be done using advanced safety equipment.

Suppressor screeningTo investigate the suppressor properties of numerous newlysynthesised PAG derivatives, a fast and efficient screeningmethod is required. Potential transients from galvanostaticcopper deposition experiments are suitable to select promis-ing suppressors for further wafer plating experiments.4,5,6

For these investigations an electrochemical cell equippedwith a platinum rotating disk is used. Copper is depositedfrom a so-called low acid electrolyte (10 g l-1 H2SO4, 50 ppmCl-, 40 g l-1 Cu2+) under constant current conditions.

At the beginning of each experiment, a thin copper film isfreshly plated without additives. Afterwards the additives areinjected in particular sequences into the plating bath (Figure4a). The corresponding change of the cathodic overpotentialis a direct measure for the impact of the additives on the cop-per deposition process.

Upon suppressor injection, the cathodic overpotential isincreased in order to maintain the predefined current. Thelarger the potential difference compared to the copper dep-


plating in microelectronics

Nucleophilicstarter molecule

Alkylene oxidemonomers

+

O O O

R

etc.

Catalyst

Polymerisation starterO

O*

R

m

Suppressorfilm formation

Suppressordeactivation

Ove

rpot

entia

l U

Time

Electrolyte baseline

suppressor injection

SPS injection

ΔU

ΔU

Weak suppressorlow ΔU

Strong suppressorhigh ΔU

a

b

ECD ECD

Figure 3 - Building blocks for PAGs

Figure 4 - Typical transient experiment for suppressor screening (a) & SEM images of 32 nmtechnology water substrates (centre) & after plating with weak (left) and strong (right)suppressors





osition from an additive-free plating solution (ΔU), thestronger the suppression by the PAG derivates. Compoundsshowing the largest increase in overpotential were expectedto be the most promising candidates to show good fillingresults in 32 nm and following node features.

However, to predict a good superfilling behaviour thecompetitive action of suppressor and accelerator must also betaken into account. This is simulated by injecting the acceler-ator into a suppressor-containing plating bath. For the super-filling mechanism it is indispensable that the acceleratorshould be able to deactivate the suppressor film.

Thus, after the addition of the accelerator to the solution adecrease of the cathodic overpotential is expected.Accordingly, only PAG derivatives showing the overpotentialsequence shown in Figure 4a have been selected as promis-ing suppressor candidates. SEM images of 32 nm test struc-tures plated with a weak and a strong suppressor demon-strate that a strong suppression results in void-free filling(Figure 4b).

Leveller additivesIt has been demonstrated that defect-free filling of 32 nmfeatures can be observed by using a combination of a tailor-made PAG derivative and SPS. However, to observe thedesired plating result a third additive, the so-called leveller, isrequired.

When the feature is filled, the accelerator species concen-tration is locally very high on top of the features, leading toa significantly higher copper thickness over dense lines com-pared to an unstructured area (Figures 5a & 5c). Levellermolecules interact with the negatively charged acceleratorcompound. This deactivates the accelerator molecules, thusprohibiting the mounding phenomenon after superfilling(Figures 5b & 5d).

The addition of a leveller is essential, since mounding cangreatly disturb the subsequent CMP process. Besides itsmain function of generating a homogeneous thickness distri-bution, the leveller must provide a low surface roughness and

a mirror-finish appearance in the plated copper over theentire wafer. Without a proper leveller, a rough surface isobtained and the wafer appears hazy.

The challenge in developing leveller compounds for ≤ 32nm technologies is to find the right balance between goodlevelling behavior and a low interference with the superfill.Typically, leveller molecules are positively charged monomer-ic or polymeric nitrogenous compounds such as dode-cyltrimethylammonium chloride, polyethylenimine orpolyvinylpyrrolidone.7,8,9

New generation leveller candidates were tested for theirlevelling behaviour in the presence of an optimised suppres-sor and SPS. The experiment revealed several that did notshow any substantial interference with the superfill (Figure 5f)and provided excellent levelling properties (Figure 5d). Forcomparison, Figures 5c and 5e show the fill results of anadditive package containing an inappropriate leveller, caus-ing void formation within the trenches and unwantedmounding.

In conclusion, synthesis and step-wise screening of a hugevariety of tailor-made suppressor and leveller compoundsresulted in the appropriate additive packages fulfilling therequirements for the 32 nm and 22 nm technology. Basedon our previous results, we are now developing additivepackages for even smaller technology nodes.

* - Also contributing to this article were Drs Roman Benedikt Raether & AlexanderFlügel. The authors with to thank Drs B. Baker-O’Neal, Q. Huang, and J. Kellyfrom IBM’s T.J. Watson Research Centre, Dr C. Emnet, Dr A. Haag, M. Hahn, H.Hörhammer, R. Leutschaft, Dr M. Martin, Dr D. Mayer, Dr A. Panchenko and A.Wagner of BASF and Dr P. Broekmann from the University of Bern for their con-tribution to this work.

For more information, please contact:Anke HaufGlobal Communication - Inorganics DivisionBASF SECA/K- E100D-67056 LudwigshafenGermanyTel: +49 621 60 43776E-mail: [email protected]: www.basf.com

References:1. R. Andricacos, C. Uzoh, J.O. Dukovic, J. Horkans & H.Deligianni, IBM J. Res. Develop. 1998, 42 (5), 567-574.2. International Technology Roadmap for Semiconductors:http://www.itrs.net.3. A. Flügel, Copper Damascene Process: From the Wafer to theAtomic Scale, DPG Frühjahrstagung, Regensburg 20104. A. Spänig, M. Arnold, C. Emnet, M. Hahn, A. Wagner, C.Röger, D. Mayer, Q. Huang, B. Baker-O’Neal, K. Kwietniak, J.Kelly & P. Broekmann, Impact of Current Density on CopperDeposition Kinetics, ECS 216th Meeting, Vienna, 20095. P. Broekmann, Adsorptive SPS Dissociation within the c(2 x2)-Cl Matrix on Cu(100) Under Reactive Conditions, ECS 217thMeeting, Vancouver, 20106. R. Akolkar & U. Landau, J. Electrochem. Soc. 2004, 151(11),C702-C7117. S.-K. Kim, D. Josell & T.P. Moffat, J. Electrochem. Soc. 2006,153 (12), C826-8338. S.-K. Kim, D. Josell & T.P. Moffat, J. Electrochem. Soc. 2006,153 (9), C616-6229. M.J. Willey, J. Reid & A.C. West, Electrochem. Solid-StateLett. 2007, 10 (4), D38-41

Figure 5 - Mounding (a & c) levelling (b & d) behaviour & incomplete (e) & perfect (f)superfill on a real substrate


Developments in chemistryfor printed electronicsDr Peter Harrop of IDTechEx takes a brief look at the role of the chemicals industry in the nextelectronic revolution




Imagine helicopters dropping biodegradablesmart dust on that oil slick to monitor all the ani-mals and pollution in detail. It self-organises

electronically like the internet to send the informa-tion back and each speck gets its electricity fromthe sun and waves without batteries.

Imagine superwoman, created by smart textilesand implants. Or dream of an electric car that iscompletely coated with transparent layers. Thesevariously act as solar cells creating electricity, bat-teries storing it and electronics and electrics man-aging everything required by the car.

You have entered the world of printed electron-ics and there is more, much more, to come, evenbending light to make things invisible. Then wehave mimicking the synapses of the human brainwith the printed TiO2 ‘memristors’ first demon-strated last year and making edible and stretchableelectronics.

Recently, many patents have been registered onthese capabilities, based on actual demonstrations.More important than the silicon chip 40 years ago,this new electronics potentially includes printedelectronics and electrics. What is thin film today isprinted tomorrow. And the chemists are holdingthings up.

There are many successes on the way to whatwill be a $300 billion business, incorporating atleast a $100 billion materials business 20 yearsfrom now. Printed silver already gives us water-proof, roll-up, membrane keyboards, complexantennae moulded into the plastic of cars and sen-sors that record which tablet you took and whenfrom your blister pack.

Together with printed resistors, we get the bat-tery tester in the Duracell battery. Conductiveprinted polyanilene and polythiophene provideantistatic and RF shielding on plastic film.

Recent progress In the last year, three companies have announcedways of printing very conductive copper withoutproblems from the insulating oxide. That will savemoney and avoid the need to use a biocide.Manganese-doped zinc sulphide AC electrolumi-nescent layers are printed to give us huge, flexible,screen-printed, animated posters and the T-shirtthat flashes a sequence of images when you entera WiFi zone.

This technology is now being used in repro-grammable posters that have light-emitting mov-ing images, sound and even the emission of anaroma when you approach. Partially printed elec-trophoretic displays, based on carbon, TiO2 andglycerine, need no electricity unless the image is

being altered, so they have been the basis of e-readers, shelf-edge displays and even wristwatches.

Flexible versions with printed polythiophenetransistor arrays on the back are coming to marketthis year. InGaZnO semiconductors are the basis oftransparent printed transistor circuits and we areprinting ZnO nanowires and lead zirconate titanatepiezoelectric to generate electricity for small print-ed electronic devices. Carbon nanotube inks formsuperb semiconductors, conductors and other lay-ers in the laboratory and some are transparent. C60

buckyballs enhance the performance of printedorganic photovoltaics (OPV).

Most of the potential market for the new elec-tronics is for flexible and conformal things, such asthe large display that will unroll from your mobilephone then snap back when it is not needed.Photovoltaics (PV) must be pasted across thebumpy, angled outside and inside of buildings.

Organic materials are attractive for much of thisbut the polythiophenes and other chemicals theyemploy are still very reactive and inefficient in con-verting light to electricity. For example, the newprinted organic solar bags that charge your phonehave only a one-year guarantee. Printed inorganicversions based on CdTeCdSe, GaAsGe or copperindium gallium diselenide or TiO2- and ruthenium-based dye and iodine-based electrolyte are moreenduring but possibly more expensive to make.

Organic light-emitting diodes (OLEDs) are a thinfilm form of display with no pollutants, very lowvoltage for safety and superb moving colourimages. These light-emitting displays are successfulin some mobile phones and available in a tinynumber of television sets but they are tediouslymade by vacuum processes sandwiched in glass.

We are trying to move from monomers to solu-ble oligomers and polymers for flexible OLEDs.When printed on plastic film, their life is often onlya few weeks yet we need the lower cost of printingand the flexible displays that result. They will go onbillions of medical disposables and trillions of con-sumer packaged goods.

Chemists need to produce more stable activematerials in these displays and better barrier layers(typically one oxide or nitride layer, then an organ-ic layer for planarisation, these ‘dyads’ beingrepeated if necessary. Can they have getteringaction as well as impermeability?). Barrier layers arealso needed to make OPV on buildings, boats andaircraft a long-lived success.

Thin film and fully printed batteries are findinguses as back-up and energy harvesting power sup-plies, for example. NEC is bringing a transparent,flexible organic battery to market in Japan.

The polymer developed by the researchers con-sists of a simple polystyrene backbone with arylpendant groups known as ‘galvinoxyl’ groups.

IdTechEx_p27-28_scm07_IdTechEx 7/14/10 10:03 AM Page 27




These support an oxygen radical, which gives upits electron under redox conditions. When it isplaced in a battery arrangement with an electron-accepting polymer, electrons can flow around thecircuit to provide power.

In 2009, initial tests in a cell with a lithiumanode revealed that the galvinoxyl polymer’s per-formance was stable for at least 500 charge-dis-charge cycles. Such batteries, printed on polyesterfilm can be charged in one minute. Redox reac-tions are also the basis of printed electrochromicdisplays but their life needs to improve.

Role of chemistryLet us now summarise the trends, challenges andfuture of this exciting new opportunity for thechemicals industry. Here we have a huge numberof opportunities for premium priced specialitychemicals and associated services but also for highvolume materials.

This is mainly a story about inorganic materialstoday but there will be a more even split of organ-ic, inorganic and composite materials in the future.Chemicals companies with the necessary virtuositywill have an advantage in terms of pollution, price,morphology and materials.

The new electronics is not always environmen-tally friendly and that needs to improve. If possible,we should replace bismuth in thin film thermo-electrics, cadmium in CdTe thin film PV and lithi-um in some batteries that a child may chew.

Carcinogens and alleged endocrine-disruptingmaterials used in the manufacture of some organ-ic inks are troublesome too.

The new electronics often employs materialswhere there are ample crustal resources but extrac-tion is troublesome leading to price hikes. Think sil-ver conductors (copper is not the whole answer; it isno longer approved for all contact with food and itpoisons an OLED), indium (ITO transparent elec-trodes are currently used for most forms of displayand PV, printed CIGS PV and so on), neodymium(thin film magnets and motors) and lanthanum(NiMH batteries).

Almost all forms of printing are employed inprinted electronics. Often, several printing technolo-gies are employed to produce one device. Each callsfor a different morphology and rheology.

Fully dissolved metals are sometimes used for inksbut they need to be more affordable. Nanosilver inkcan be annealed at low temperature so that low costplastic films or paper substrates suffice.

Its price premium may now have fallen to thepoint where the resulting conductive pattern islower cost that that printed conventionally,because less silver is used, but more progresswould be welcome. PVDF derivatives are favouredfor printed ferroelectric memory but better techni-cal parameters would be welcome, even the avoid-ance of destructive read write.

Flexible smart substrates are increasingly usedto leverage the printed circuits on them. For exam-

ple, electroactive polymers give us reprogramma-ble Braille and haptic touch switches, even microp-umps. Some PVDF films are electrets in micro-phones. PVDF film acts as a piezo eel underwaterand a piezo flag in the wind, generating electricity.

The New University of Lisbon makes the papersubstrate of a printed InGaZnO transistor doubleas the gate dielectric. Other substrate films at ITRITaiwan act as ultrasound emitters and detectorswhen printed with electronics. New smart sub-strates are welcome and there should certainly bemore work on paper. For example, KimberleyClark has carbon-loaded paper that acts as a heat-ing element or sensor network.

Even dumb substrates need improvement. Thefavourite substrate for printed electronics is biaxial-ly oriented, surface-treated polyester film but PENor something similar is needed where greaterdimensional stability and temperature range arevital, if only to tolerate the annealing of sub-opti-mal inks. However, its price multiple needs tocome down.

Tel +44 (0)1435 873062 • Fax +44 (0)1435 [email protected] • www.scientificupdate.co.uk

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IdTechEx_p27-28_scm07_IdTechEx 7/14/10 10:03 AM Page 28

Sustainability was the theme of Wacker Chemie’s international press briefing earlier this year

Keeping things going


Sustainability


“Wacker is fully commit-ted to sustainabledevelopment and has

considered it an integral goal of pro-duction and business process formany years,” said Jörg Krey, seniorvice-president of corporate develop-ment, who was speaking at theGerman chemicals company’s inter-national press briefing this March.

Speaking more specifically aboutproduction issues, Dr Klaus Blum,vice-president of chemical services atthe main site at Burghausen, nearMunich, echoed Krey. “Sustainabilityhas been part of Wacker’s productionand business processes for manyyears now,” he said.

Sustainability is big news thesedays, however, so similar wordsmight be expected from just aboutanyone in their positions. But whatdoes Wacker Chemie really mean byit and what is it actually doing to livethe concept? The briefing gavesome answers, both globally andspecifically for Burghausen, as wellas for the different divisions andtheir products.

Wacker, said Krey, is convinced“that chemistry makes a vital contribu-tion to global progress and sustain-able development”. The company’saim, therefore, is to balance the eco-nomic, environmental and socialaspects of sustainability (Figure 1),making it the basis of long-term busi-ness success. This involves, amongother things:

• Ongoing high spending on envi-ronmental protection

• Safe operation of plants

• Product safety

• Open dialogue with stakeholders

• Business success through highvalue products

The company has been involved inthe Responsible Care initiative since itstarted in 1991 and joined the UN’sGlobal Compact in 2006. This is nowthe world’s largest sustainability initia-tive, with over 4,700 member compa-nies and participants from 130 coun-tries committing themselves to pro-moting human rights, labour stan-dards and environmental protectionand to fighting corruption.

Like health and safety, Krey contin-ued, environmental protection is acore component of all Wacker’sprocesses. It begins at the productdevelopment and planning stagesand, in line with Responsible Careprinciples, involves taking measuresthat go beyond what is legallyrequired. The company aims to con-serve resources and decouple energyconsumption and waste generationfrom production volumes.

As part of its product steward-ship responsibility, Wacker ensuresthat the findings of risk assessmentsare implemented speedily and pro-vides material safety data sheets(MSDSs) on all of its products - a totalof some 54,000 MSDSs in 32 lan-guages - even though only 40% ofthe products require them by law. Ithas also pre-registered over 7,000substances under REACH and sub-mitted 45 registration dossiers to theEChA in 2009.

Workplace, plant & transportsafety “form the basis for uninter-rupted production”, Krey said. Thisinvolves extensive safety and riskanalyses of plants from the designstage to commissioning and regularseminars on plant and work safetyand explosion protection. Morespecifically, Wacker launched its‘Fresh Impetus for Work’ initiative in

2007, with the aim of reducing work-place accidents and extended this tonon-German sites last year.

There is still some way to go, sincelast year the company had 4.0 acci-dents/million hours worked, slightlyabove the ICCA’s world average of3.65. However, this was well belowthe German average of 9.1, whileBurghausen’s rate of reportable acci-dents in 2009 - 1.3 per 1,000 employ-ees was well below the chemicalindustry rate of 14.7 in 2007

In terms of transport, sustainabilitymeans ensuring that hazardousgoods are transported by rail wherev-er possible and that hazardous goodsvehicles are always checked beforeloading, with non-compliant ones notbeing loaded. Shippers of hazardousgoods for Wacker are audited verytwo years using internationally validat-ed systems like CEFIC’s SQAS.

Finally, as well as corporate citizen-ship activities, Krey cited the stepsWacker takes to “create the right con-ditions for all employees to developtheir abilities to the full” through train-ing and advancement programmesand initiatives to balance work withfamily life. The company has a signifi-cantly lower employee fluctuation ratethan most - 0.7%/year in Germanyand 2.3%/year worldwide.

Burghausen, as site communica-tions manager Klaus Millrath pointedout, is the largest chemicals site inBavaria. It employs nearly 10,000people in about 130 production facil-ities over an area of 2.3 km2 that

ship out 900,000 tonnes/year ofproduct. All of the divisions - WackerSilicones, Wacker Polymers, WackerBiosolutions, Wacker Polysilicon andSiltronic - are present, as are somesubsidiaries and some operationsthat have been sold to others.

“All production and service unitswork closely together in a technologi-cally and economically integrated sys-tem, each observing the same stan-dards of EHS protection,” Millrathsaid. Indeed, added, Blum, this inte-grated management system (IMS) iscritical to sustainability in productionat Burghausen.

The IMS regulates all workflowsand responsibilities, taking equalaccount of productivity, quality andEHS and is based on legal provisions,national and international standards,such as ISO 9001 and 14001. Overhalf of Wacker’s IMS regulations,Blum noted, govern processes forplants, workplace and product safety,environmental protection and occupa-tional health and safety.

The integrated production systemat Burghausen is based on siliconeand ethylene as starting materials,which offers ecological as well as eco-nomic benefits in terms of the imme-diate reuse and recycling of materials,production intermediates and by-products. Figure 2 illustrates the loop.

Four starting materials - silicon,methanol, hydrogen and sodiumchloride - are used to make over3,000 silicone products, pyrogenic sil-ica and polysilicon at the site, while

Society

Environment Economy

Tolerable Equitable

Sustainable

Viable

Figure 1 - Balancing the pillars of sustainability

Burghausen is Wacker’s main site and the largest chemicals site in Bavaria

Wacker_p29-31_scm07_Wacker 7/14/10 10:04 AM Page 29

Sustainability



the integrated ethylene system gener-ates organic intermediates, polymerdispersions and dispersible powderpolymers. Likewise, HCl, which isused to make many chlorine-contain-ing intermediates is recovered andreturned to the production loop.

Energy is another critical elementof production sustainability, Blum con-tinued. The chemicals industry is oneof the most energy-intensive of allindustries, accounting for 20% of allindustrial power consumption inGermany, while Burghausen aloneconsumes 1.7 billion kWh/year, aboutas much as a mid-sized city. Efficientuse of electricity is vital for climateprotection and competitiveness.

For this reason, Wacker launchedits ‘Power Plus’ initiative atBurghausen and the other mainGerman site at Nünchritz in 2006,striving for a 10% reduction in specif-ic energy consumption by 2009. Todate, 36 plants at the two sites havebeen examined and potential savingsin electrical energy and steam identi-fied of 14.3% and 22.8% atBurghausen and 18% and 50% atNünchritz. The programme has nowbeen extended to the Cologne site.

Both Burghausen and Nünchritzhave combined heat and powerplants, which are 80% fuel-efficient,far more than most power generators.Burghausen also takes 270 millionkWh/year of hydroelectric power gen-erated by a Wacker subsidiary compa-ny, Alzwerke on a nearby river, there-by saving 58,700 tonnes of naturalgas consumption and preventing162,000 tonnes of CO2 emissions.

Combined, these power sourcesgenerated 1.4 million MWh of elec-

tricity in 2008, about 60% of totalelectricity needs at the two sites.Burghausen also uses ion exchangemembrane electrolysis in chlorinemanufacture, using 25% less energythan the mercury or asbestosprocesses.

Other key issues at Burghauseninclude water and waste disposal.Biological treatment is used to purifywaste water, while technologicalimprovements in the cooling watersystem have saved some 4,700m3/year of water. In 2008, Nünchritzdeveloped a mew method for recy-cling some 1,000 tonnes/year of pyro-genic silica that used to be landfilledfor use as a building additive.

Because the North Sea ports ofHamburg and Bremerhaven are some400 km away, Wacker uses theSchütz container system to reduceshipments. In addition, 600,000km/year of transport needs havebeen eliminated by having the suppli-er open a plant near to Burghausen.

There were also presentationsfrom most of the operating divisionsof Wacker at the briefing. Each ofthese, the company claims, con-tributes in different ways to sustain-ability in their production atBurghausen and other sites and,more importantly, to much widersustainability issues in the world.

Perhaps foremost among them isWacker Polysilicon, which is one ofthe world’s largest makers of hyper-pure photovoltaic (PV) silicon. As sen-ior marketing manager Dr WolfgangStorm pointed out, we must makeincreasing use of PV if we are to relymore on renewable energy in orderto put a lid on global warming while

meeting ever-increasing energydemand.

Mono- or multi-crystalline silicon(c-Si) cells represent by far the mostimportant technology on the PVmarket, Storm added, and willremain so. This had 88% of the totalin 2008 and is edging out α- and µ-Si on cost grounds. Cadmium tel-luride (CdTe) is the only serious com-petitor but the cost advantages itseemed to offer at first are levellingoff; CIGS and organic PV are still inthe development phase.

By, for example, improvingprocess efficiency, cutting costs andintroducing its advanced polysilicondeposition technology, Wacker hascontributed to making solar panelsmore economically viable. The pay-back period for the initial investmentis now about one year for productswith an expected lifetime of 25-35years.

The energy required to producepolysilicon is the single largest por-tion of energy usage by it. In thiscontext, Storm said, Wacker’s successin reducing by 50% the energyneeded to make a tonne of it is a“significant contribution”. Net energygeneration has risen to 7,000mWh/tonne of polysilicon, whilesome 6,000 tonnes of CO2 aresaved compared to the cost of burn-ing coal to generate electricity.

In addition, the cost of PV systemshave fallen by 50% in the past threeyears. As a result, ‘consumer grid par-ity’, the point at which the cost of gen-erating solar energy is the same asbuying it, has been reached in somesunny areas, notably Italy and Hawaii,and is looming close in others.

Virtually all major countries, withRussia the only notable exception,are supporting the growth of the PV

industry via feed-in tariffs or prepar-ing to. The industry association fore-casts that solar energy markets willgrow by 45%/year from 2007 to2013, creating millions of jobs aswell as contributing to sustainabledevelopment.

Dr Bernd Pachaly, vice-president ofengineering silicones at WackerSilicones, described the use of sili-cone elastomers, which representabout 20% of the global siliconesmarket, in high-tech applications.Their properties, he said, “make theminteresting for a wide range of sus-tainable applications” - notably theirheat stability, low glass transition tem-perature, long-term flexibility and sta-bility, biocompatibility, physiologicalinertness and low flammability.

Silicone elastomers are increasing-ly used in the production of LEDs,the use of which can massivelyreduce energy consumption andCO2 generation. Thanks to theirheat- and UV-resistance and allowinglead-free soldering at over 260°C.Certain Wacker grades are alreadyused to encapsulate LED chips andproduce lenses, while the new highperformance Lumisil silicones enableoptical lenses for LEDs to be pro-duced directly onto the chip in a sin-gle step for the first time.

In a similar vein, said Pachaly,Elastosil Solar 3210 was designedspecifically for optical lenses andmouldings in high-concentrated PVsystems. These are an alternative toconventional PV technology in whichthe sunlight is bundled and focusedonto highly efficient cells via crystal-clear silicone Fresnel lenses.

Silicone elastomers are also used inpower generation, transmission anddistribution, in applications rangingfrom insulation to coatings, arresters,

Figure 2 - Integrated production system at Burghausen

High-concentrated PV systems are new markets for polysilicon

Rock salt

HCl-burner

CA-membraneplant

Cl2 H2Electricity

Base-chemicalsSalesProductsIntegrated chemical production

Chlorinestorage

chlorine

Met

allu

rgic

alsil

icon

Metallurgical silicon Methanol

HCI

HCI

HCI

Silanes

SiCl4 Pyrogenic silica

Caustic soda

Silicones

Specialities

HCI

Trichloro-silane

HyperpuresiliconPolysilicon

Production


Sustainability



cables and transformer fluids. Siliconerubber composite insulators consume50% less energy and release 75% lessCO2 than comparable porcelain insu-lators, making them an increasinglyattractive option.

Finally, Wacker has recently devel-oped a new generation of UV-acti-vated silicone elastomers, whichaddition-cure rapidly with minimalenergy input at room temperature.This means that their reactivity canbe controlled within a broad time slotand processing window, withoutdepending on the intensity or dura-tion of the UV radiation, thus allow-ing shorter cycle times and higherproductivity.

“The use of silicones can oftengreatly boost the efficiency of produc-tion processes, both economically andecologically,” Pachaly concluded. “Thedurability of silicone elastomers makesa considerable contribution towardsthe efficient use of resources.”

The construction industry is anoth-er major consumer of energy andgenerator of CO2, as well as a majorclient of several divisions of Wacker,according to Peter Summo, vice-pres-ident of construction polymers atWacker Polymers, and Bernd Judas,vice-president of construction siliconesat Wacker Silicones.

The mega-trends of urbanisationand mega-cities, combined withincreasing population and pressureon resources mean that more sus-tainable building is vital. Summo andJudas noted figures from a DeutscheBank study suggesting that emissionsfrom buildings account for 40% of allemissions and that applying energyefficiency measures could save five

times more energy than that pro-duced by all the nuclear powerplants in Germany in 2007.

In this context, Vinnapas dis-persible polymer powders have amajor role to play. Such polymericbinders are vital to the use of exter-nal insulation and finish systems(EIFs) in both new and refurbishedbuildings. These, said Summo, “arethe simplest and most reliablemethod of conserving energy forbuildings over the long term”,because better insulation means lessenergy is needed to create a com-fortable indoor climate, whatever theconditions outside.

Polymer-modified sealing slurriesare also based on Vinnapas powders.These are easy to use and protectstructures from water damage byboth preventing water ingress andconserving water in impregnatedwater channels and reservoirs.

Finally, Vinnapas powders makepossible the thin-bed technique oflaying tiles, using 3 kg of dry mor-tar/m2 instead of the 10 kg of adhe-sive used in the thick-bed techniquethat still prevails in the developedworld. Thus tilers can work fasterwhile saving on material consump-tion and reducing CO2 emissions by50%. Many Wacker customers,notably BASF, Henkel and Mapei,are already working on productdevelopment based on these sustain-able offers.

Silicones also play a part in thefunctional coating systems that pro-tect modern façade coatings againstmoisture and harmful environmentalinfluences, according to Judas.Indeed, silicone resin emulsion paints

(SREPs) are among the most effec-tive of all, because they form ahydrophobic film on the façade thatis also water vapour-permeable,ensuring that damp masonry driesfaster.

Dr Christopher Winterhalter,director of chewing gum at WackerBiosolutions - the recently renamedWacker Fine Chemicals - looked atsustainable biotech products andprocesses. His main emphasis was onthe use of two corn-based products,cyclodextrins and the natural aminoacid cysteine, in both of which thecompany is a world market leader.

A major recent innovation, hesaid, was the development of an“extremely efficient and environmen-tally compatible” fermentative pro-duction method for cysteine fromplant-based raw materials using E.coli bacteria. This is increasinglyreplacing the extraction of cysteinefrom human hair, pigs’ bristles andpoultry feathers.

The new technique enables 90% ofthe bacterial cysteine to end up in thefinal product, as opposed to 60%. Theamount of hydrochloric acid need toextract it is reduced by 96% from 27kg/kg of final product to 1. Fractionalcrystallisation and electrolysis are nolonger needed and boiling tempera-tures are reduced to 30-35°C.

The final product, said Winterhalter,is vegetarian-grade, kosher and halal.It is also ideal for food and pharma-ceutical applications because any riskof contamination by human or animalpathogens is avoided. In addition, theresidues, of which there are fewer, cannow be used as fertilisers.

White biotechnology in general,added Dr Fridolin Starry, senior vice-president of corporate R&D, is “a keytechnology for innovative and sustain-able products and processes in thechemicals industry”. This includeschemical products based on biomass,the increasing use of biocatalysis inprocess chemistry and processing theby-products of biorefineries.

With rising petrochemical prices andimprovements in technology, “moreand more processes will become eco-nomically competitive for bulk chemi-cals” based on such superabundantresources as glucose, straw and ethanol.Indeed, they already are for some highvalue products like vitamin B2, antiobi-otics, cyclodextrins and cysteine.

Wacker has therefore implementedseveral R&D projects for the biotechproduction of bulk chemicals. Itlooked at three routes to biogenic

acetic acid and is now operating 500tonnes/year pilot plant that uses theACEO process to ferment bioethanoldirectly via gas phase oxidation. Thiswas preferred to the more indirectroutes via fermentation to butanedioland homoacetate fermentation.

The process, Starry said, achievesexcellent yields and selectivities yet isstill completely energy-autarkic.Moreover, it can use low quality feed-stocks with >25% EtOH. In the sixmonths of operation, it has exceededexpectations in terms of:

• An efficient and robust process

• No need for exotic engineeringmaterials

• Known scale-up engineering data

• Low capex requirements

• High variability for different ethanolquantities

• Bioethanol costs strongly influenc-ing production costsProduction from this route means

that the refinery can be located any-where while still being competitive onprice. Finally, the bioethyleneobtained could be suitable forWacker’s vinyl acetate ethylene andvinyl acetate monomer (VAM) pro-duction. VAM is, indeed, another bulkchemical that the company is evaluat-ing for biotech production routes.

Above all, Wacker feels that sus-tainability makes sense at every level.“Chemistry makes a vital contribu-tion to global progress and sustain-able development,” Krey said. Atpresent, it is saving two tonnes ofgreenhouse gas emissions for everytonne emitted and that ratio shouldbe 4:1 by 2030.

Moreover, he concluded, sustain-able chemistry also makes economicsense. “Mega-trends such as energy,urbanisation, construction, digitisationand rising living standards will increas-ingly stimulate demand for sustain-able products and technologies.” TheBRIC countries alone will generate acompound annual growth rate of3.7%/year over the next 25 years forsuch products, so the potential is vast.

For more information, pleasecontact:Florian DegenhartCorporate Communications Wacker Chemie AG Hanns-Seidel-Platz 4 D-81737 München Germany Tel: +49 89 6279-1601 E-mail:[email protected] Website: www.wacker.comVinnapas polymers have many contributions to sustainable construction



Dennis McGrew of Genomatica outlines the case for directly produced, drop-in bio-based replacements for traditional manufacturing methods

Sustainability

In the last 18 months, the chemicals industryhas made significant strides toward more bio-based production. One year ago, a survey con-

ducted by Genomatica and ICIS showed that 57%of industry executives said their companies shouldreduce their exposure to the petroleum-basedcommodity market. Companies also acknowl-edged that their customers have expressed realinterest in chemicals based on renewable materi-als.

More than half of the executives in the survey,however, said that cost was the most prohibitivepart of a sustainable chemicals programme.Consumer attitudes, volatile petroleum marketsand global demand contraction have convergedfor a unique moment of interest and demand forsustainable chemicals, but cost continues to be thekey barrier to adoption.

If capacity rebounds in the next three to fiveyears, as some analysts predict, it will present aninteresting opportunity to introduce new processtechnologies that use renewable feedstocks tomanufacture chemicals. These new processes candrive the start of a transformation of the chemicalsindustry.

However, helping the industry to transitionfrom petroleum-based feedstocks to renewablefeedstocks will not happen overnight. As shown inthe survey, common wisdom holds that transition-ing to a more sustainable industry will raise costsand further squeeze tight margins.

Making the industry more environmentally sus-tainable at the cost of economic viability is not anoption. Genomatica believes strongly that sustain-ability must come at a lower cost and that innova-tive biotechnology can deliver sustainable solu-tions at lower costs, especially when direct pro-duction routes eliminate as many intermediateprocessing steps as possible and the resulting

materials are equivalent to conventional ones usedtoday, enabling them to be dropped into existingdownstream value chains.

Metabolic engineering platformTo fulfill this daunting goal of low-cost sustainabil-ity, our research teams have explored hundreds ofroutes to dozens of products. Genomatica’s coretechnologies for metabolic engineering, combinedwith our laboratory and process engineering capa-bilities, have enabled us to explore a broad port-folio of processes to generate a range of chemicalintermediates.

Early assessment and IP around platform mole-cules like succinic acid and 3HP were de-empha-sised in favour of more direct production routes toexisting, large chemical intermediates like 1,4-butanediol (BDO). Our other ongoing efforts alsoinclude various acrylates, polyamide (PA, or nylon)intermediates, solvents and surfactants. Publishedpatent applications demonstrate the breadth ofroutes available, with development priority givento those with the best opportunity to deliverbreakthrough cost reductions of >25% over thebest available conventional technology in large,growing chemical intermediate markets.

Challenges with indirect routes In August 2004, the US Department of Energy(DOE) published a study intended to evaluate andcompare more than 300 molecules from the pointof view of technological feasibility, size of potentialmarket and interest to the chemicals industry. Itidentified priorities for the top 12 chemicals ofgreatest interest.

These 12 are often called platform molecules,because they may serve as a platform for produc-ing a variety of derivatives. However, they gener-ally provide an indirect route to the chemical inter-

mediates that are large consumers of fossil fuelstoday. Such routes face several potential chal-lenges that may ultimately affect economics.

Unwanted by-products are often generated thatimpact not only costs, but also the process’s envi-ronmental footprint, while additional processingsteps typically require more unit operations withthe inherent added capital, energy and operatingexpense, as well as creating the potential for yieldlosses.

Finally, the chemical intermediates purportedlyderived from these platform molecules often havesubstantially larger markets than the platformchemicals themselves, requiring large infrastruc-ture investments to reach sufficient economies ofscale to make a significant impact on fossil fueluse.

Unintended consequencesA concern, especially for larger-scale chemicalintermediate production, is the potential for unde-sirable co-products from indirect productionroutes. Organic acids, some considered as poten-tial platform molecules, are an example of this.

Lactic acid can be produced from bio-basedfeedstocks through fermentation but requiresdirect acidification, esterification and hydrolysisthrough reactive distillation to purify and providea useful chemical intermediate. Direct acidificationproduces large quantities of gypsum co-product,which may not be pure enough for industrial use.

As processes scale up, even a relatively minorwaste stream can become problematic, addingdisposal costs and reducing yield. Improvementsin technology may substantially reduce undesir-able co-products, but will likely not eliminate thementirely.

Platform chemical routes like organic acids maybe effective for some small speciality chemicals or


Getting to the point: Direct bio-base

Fermentation

Hydrolysis

Lime

SugarsDirect

Acidification Esterification

Lacticacid

Water

Sulphuricacid

Gypsum

Alcohol

Water

Ester

Figure 1 - Traditional route to lactic acid

Genomatica_p32-34_scm07_Genomatica 7/14/10 10:06 AM Page 32


Sustainability

niche ‘green’ markets, but for larger volumechemical intermediates like 1,4-BDO, acrylates ornylon intermediates, the waste products couldbecome problematic.

Lactic acid also shows the challenge of multipleunit operations required to isolate and purify it asa raw material for subsequent chemical conver-sion to the targeted chemical intermediates(Figure 1). Further, impurities associated with itsproduction can be problematic for downstreamproducts, affecting yields and separations, espe-cially as one strives for lower costs. These chal-lenges may also manifest themselves for otherorganic acids developed as platform chemicals.

Keeping it simpleWhilst platform molecules may indeed providebio-based routes to various chemical intermedi-ates, the additional necessary steps run counter tothe goal of a low-cost solution. To foster wide-spread adoption of sustainable chemicals, the newprocesses must cost less than traditional methods.

We see our direct production route to 1,4-BDO(Figure 2) as a prime example, eliminating theneed for the isolation and purification of succinicacid and the subsequent high-temperature andhigh-pressure steps for BDO conversion via cat-alytic hydrogenation. We estimate that the addi-tional processing steps between succinic acid andbutanediol could add at least 20 cts/lb (€0.36/kg)to the cost of the final product.

In both academic journals and media outlets,there is concern that succinic acid production hasnot yet reached economic competitiveness withtraditional production methods.1,2 Most sourcessay the cost of separating and purifying it from thefermentation broth is the largest barrier to eco-nomic production for most applications.

For the large global PA market, we have filed apatent application for bio-based direct route toseveral intermediates, potentially opening up fullybio-based PA 6 and PA 6,6. We typically filepatents on a range of routes, but pursue only themost direct ones, those that can be achieved in asingle organism and the simplest possible process.

We achieve this through metabolic engineeringand genetic modification.

By contrast, many of the other approaches forpursuing bio-based nylon routes are indirect pro-duction routes through platform chemicals includ-ing lysine, a common bio-based amino acid. Forinstance, researchers at Michigan State Universityhave patented a process for converting L-lysinefrom natural materials to �-caprolactam, a precur-sor to PA 6, in a handful of processing steps witha yield of about 75%. The �-caprolactam is thenpolymerised into PA 6, which has a huge globalmarket.

Genomatica’s proposed routes have significant-ly fewer steps and those steps are simpler, espe-cially in the separations of intermediates anddesired end-products (Figure 3).

Industrial inertia dictates that a simpler replace-ment technology will spread faster through theindustry where the simplicity leads to lower costs.Building replacement processes with the mini-mum number of unit operations for current large-market chemical intermediates is vital. Instead ofrequiring additional processing steps and addi-tional capital investments, more direct productionroute will ease adoption when compared to indi-rect methods.

Leveraging infrastructureThe effective and rapid transformation of thechemicals industry toward greater production ofbio-based materials will require leveraging exist-ing infrastructure to the greatest extent possible.Historically, substitutes for existing chemical inter-mediates or polymers have required substantialchanges in existing infrastructure or downstreamderivative production.

These changes can create barriers to marketadoption, extending time for speed-to-scale ofnew products and offsetting economies gainedwith bio-based production. Success critically relieson performance advantages due to these barriers.

We feel that an approach with chemically iden-tical, performance-equivalent chemicals and poly-mers at lower cost than conventional processes

will be required to drive the large-scale transfor-mation of the chemicals industry. Instead of devel-oping new markets for chemicals or requiring newinfrastructure or supply chains, direct productionof existing chemical intermediates can quicklydrop into current markets and leverage substantialdownstream infrastructure that is already in placeglobally.

At present, succinic acid serves a relatively smallworld market of about 40,000 tonnes/year.Proponents contend that the market could grow100-fold if the bio-based variety is made at a lowerprice than the petrochemical method. Whilst theglobal market for lysine is substantially larger thansuccinic acid at more than 700,000 tonnes/year, itremains far smaller than the 4,000,000tonnes/year market for caprolactam.

It is difficult to believe that economical produc-tion of large-scale chemical intermediates can bedriven through these indirect routes, as a signifi-cant amount of capital will need to be invested forthe platform molecule, in addition to capital forconversion to target chemical intermediates.

Chemicals producers are making importantstrides to serve this sustainable market demandand allow the industry to diversify away frompetrochemical feedstocks. Several processes arenearing commercialisation, as small demonstrationfacilities start up and industry leaders, includingBASF and DSM, have announced the commer-cialisation of bio-based succinic acid in the comingyears.

However, most industry efforts appear focusedon lower volume specialities, green niches, likedeicing fluids, and potentially new polymers, likepolybutylene succinate, rather than as a platformmolecule for the production of BDO. While theseefforts establish more important examples of suc-cessful bio-based processes, we believe the pathto open large chemical intermediate markets isthrough drop-in, low-cost alternatives via the mostdirect production method possible.

The International Sugar Organisation’s (ISO)first industrial bio-products market study, ‘MarketPotential of Sugarcane & Beet Bio-products’,


o-based chemical productionFermentationSugar Acidification Separations Hydrogenation

Separations BDO

FermentationSugar Separations BDO

a

b

Figure 2 - Succinic acid (a) & direct (b) routes to BDO


Sustainability



charts new territory in sugar cane and sugar beetmarket analysis by focusing on the emergingopportunity for sugar-derived chemicals, polymersand bioplastics. Genomatica’s sugar-based processfor producing 1,4-BDO is presented in the‘Biobased Chemicals’ section titled as a promisingtechnology.3

Aside from bio-polyethylene, which the ISOidentifies as a key bioplastics opportunity, thereport finds that of all chemicals studied BDO has“the best potential in the near term”, in part dueto the direct nature of its production in theGenomatica process and consequent lower pro-duction costs.

BDO’s large market size, it adds, combinedwith Genomatica’s process, gives bio-based BDOseveral advantages over bio-based succinic acid,which has a significantly smaller market andrequires additional conversion to create chemicalssuch as BDO, with yield losses and cost increasesin the process.

Direct to 1,4-BDOIf a process is to produce the target chemicalsdirectly, a microorganism must be engineered toproduce the chemical and serve as an effectivebiocatalyst. Driving the titre, productivity and yieldof the process are some of the most importantmetrics to produce an economically viable, sus-tainable chemical, and organism performance iscritical to success.

If the fermentation process can produce morequickly, that lowers the overall cost of production.Genomatica uses genetic engineering and adap-tive evolution to improve the rate of productionfrom fermentation processes.

Our research teams have focused on increasingtitres as we move toward commercialisation. Thisspring, they achieved an important milestone withour flagship butanediol process, achieving over 80gm/litre titres in 30 litre fermentations.Simultaneously, we are reducing by-products andseeing improved yields.

Unlike many organisms that make a targetedchemical as a by-product of their own growth, ourtechnology platform allows us to link the organ-ism’s growth to the production of the target chem-ical. We genetically knock out the pathways to theother by-products, so the organism must produceour target chemical to survive. All of theseadvances are important and our economic modelsestimate that our process is now at least cost-com-petitive with traditional methods of manufacturing.

We continue to refine the process and we areconfident that we can achieve a significant costadvantage through an even higher titre andimproved yield. In less than two and a half years,we moved from the first detectable quantities ofBDO ever shown in a fermentation to over 80gm/litre from raw sugar (sucrose). This thresholdmatches the cost of current petroleum-basedBDO production, and we are well on our way tothe next threshold, which will give us a strong costadvantage.

We find that traditional chemicals producers arebecoming more knowledgeable and comfortableabout titre and other key metrics of bio-basedchemical production. They understand the keys toviable production and recognise both ourprogress and the power of our integrated devel-opment process.

Next stepsLooking to the future, a few more key milestoneswill mark the industry’s progress toward a moresustainable future. We have scaled our flagshipBDO process up 100-fold, as part of the prepara-tion for a demonstration plant in 2011, and haverecently shown equivalent fermentation perform-ance at both 30 and 3,000 litre scales.

Our initial engagements with existing BDOconsumers and producers indicate that our bio-based BDO is promising from both analytical andapplication standpoints. Pilot-scale production andthe demonstration plant will allow for furtherlarge-scale sampling and downstream conversion

testing to demonstrate effective use in key deriva-tive products, including PBT, PTMEG and TPU.

We have also demonstrated the utility of ourorganism and process across a variety of commer-cial feedstocks, with no apparent loss in key fer-mentation performance metrics or final productquality. As with our BDO process, the growth ofthe industry will depend on continued conversionof bio-based products to end products, compati-bility with existing derivative infrastructure andcost-effective manufacturing.

A wide range of companies are innovating tomake the chemicals industry more sustainable andto allow for the use of other feedstocks. Many dif-ferent bio-based applications will find a range ofniche markets, but a truly widespread revolutionwill require lower costs and simple conversion.Direct, cost-effective production has greaterpotential to revolutionise the chemicals industry,expanding sustainability more quickly and bring-ing increased profitability at the same time.

For more information, please contact:Dennis McGrewGenomatica, Inc.10520 Wateridge CircleSan DiegoCA 92121USATel: +1 858 362 8578E-mail: [email protected] Website: www.genomatica.com

References: 1. J.B. McKinlay, C. Vieille & J.G. Zeikus, Prospectsfor a Bio-Based Succinate Industry, AppliedMicrobiology & Biotechnology 2006, 76, 727-7402. A. Cukalovic & C.V. Stevens, Feasibility ofProduction Methods for Succinic Acid Derivatives: AMarriage of Renewable Resources & ChemicalTechnology, Biofuels, Bioproducts & BiorefiningAugust 2008, 6, 505-5293. www.isosugar.org/PDF%20files/MECAS(09)17;%20MECAS(09)18;%20MECAS(09)19.pdf

Lysine-HCIseparationsAcidification

Ion exchangeEvaporation

NeutralisationCrystallisation

Lysine cyclisation& separationsAlkalinisationSalt, solvent &water removal

Fermentationto lysine

Deamination& �-Caprolactam

recoveryAddition of KOH& NH2OSO3HAmine removal

Sublimation

Polymerisation PA6

Sugar

6-ACAseparations

pH adjustmentEvaporation

Crystallisation

Fermentationto 6-ACA

Polymerisation PA6

Sugar

a

b

Figure 3 - Lysine-based (a) & direct 6-ACA-based (b) routes to PA 6



Sustainability


Professor Franck Dumeignil of the Université Lille Nord de France presents the concept andthe objectives of the EuroBioRef project*

Within a future sustainable society, biomass isexpected to become one of the majorrenewable resources for the production of

food, cattle feed, materials, chemicals, fuels, powerand/or heat. To realise this vision, a combined coher-ent package of measures is necessary: higher overallenergy efficiency, reduced raw material consumption,a decrease in the cost of goods and the framework tomake the large-scale transition towards a bio-basedsustainable economy possible.

Such a transition requires completely newapproaches in R&D. The biological and chemicalsciences will play a leading role in building theindustries of the 21st century, while new synergiesmust be developed and established between theagricultural, biological, physical, chemical and tech-nical sciences.

This will be combined with logistics, media and IT,economy, policy and social sciences. Specific require-ments will be placed on both industry and R&D withregards to the efficiency and sustainability of raw mate-rials and product lines. The development of biore-fineries is the key to initiate this new approach in R&Dand will allow access to integrated production of thechemicals, materials, goods and fuels of the future.

Integrating biorefineriesThe development and implementation of biorefineryprocesses, i.e. the sustainable processing of biomass toa spectrum of marketable products and energy, is anabsolute necessity and key to meeting the vision of abio-based economy.

This means using the available biomass as efficient-ly as possible and with the lowest possible environ-mental impact, energy consumption, manufacturingcosts and CO2 footprint. It also requires redefiningtransformation routes and changing product specifica-

tions according to the performances and the limita-tions of the new processes.

Biorefineries can use various combinations of feed-stock and conversion technologies to produce a vari-ety of products. However, most of the existing biore-finery concepts use limited feedstocks and technolo-gies and produce only ethanol or biodiesel. They alsofocus essentially on producing biofuels, with the con-sequence of substantially reducing the added value ofthe biomass chain.

Economic and production advantages increasewith the overall level of integration in the biorefin-ery. The benefits of this derive mostly from thediversification in feedstocks and marketable finalproducts, which is missing from most currentbiorefinery concepts.

Continuous developments in the areas of feed-stocks and conversion processes (biochemical, chemi-cal and thermochemical), combined with their integra-tion with powerful downstream separations, will meanmore economically and environmentally sustainableoptions for integrated biorefineries. Such an approachwill also make it possible to spread biorefineries acrossthe whole of Europe, while adapting them to local con-ditions and resources.

Moreover, as different studies show, biobasedindustrial products can only compete through biore-finery systems where new value chains are developedand implemented. This means that new marketableproducts, like high value-added chemical or biochem-ical products, and specific high value-added biofuels,like high-energy aviation biofuels, could enhance theviability and interest of biomass.

Such is the thinking behind the EuropeanMultilevel Integrated Biorefinery Design forSustainable Biomass Processing (EuroBioRef) proj-ect, of which I am the co-ordinator. EuroBioRef was

launched on 1 March 2010 for a duration of fouryears, supported by €23 million in funding from theEU’s 7th Framework Programme.

EuroBioRef deals with the entire process of biomasstransformation, from fields to final commercial prod-ucts. It involves 28 partners from 14 different countriesinto a highly collaborative work.

The 28 include producers of biomass andadvanced biomass, such as lignocellulosic and oilcrops, as well as suppliers of pre-treatment servic-es, thermochemical reactions, catalysts andadvanced enzymes, process designers and engi-neers and final chemical and biochemical produc-ers and end-users.

Also involved are an aviation fuel refinery and a jet-engine maker, both in Poland. The sustainability of thewhole project will be analysed and optimised by socio-economic, life cycle and civil organisation analysts andproject management specialists.

EuroBioRef will focus on developing and deploy-ing a highly integrated and diversified concept withfeedstocks, technologies and processes that can bebundled to facilitate and define a new interwovenvalue chain with integrated flexible biorefinery facil-ities. These will help to develop optimised produc-tion processes yielding high value-added productsthat could be also adapted to large and/or dedicat-ed small production for application in wider regionsthroughout Europe.

EuroBioRef conceptThe watchwords of the EuroBioRef project - ‘flexibility’,‘adaptability’ and ‘multi-dimensional integration’ -show its high ambitions. The basic concept uses a newand flexible approach of combining ‘virtual integration’with proximity to both feedstock sources and productmarkets, so as to address fully:

Designing the nextgeneration of biorefineries

Variety ofBiomass

Pre-

trea

tmen

t

Cellulosic &chemicellulosic residual

materials

Integrated demonstration of building blocks of highvalue added bioproducts

High value added chemicals, polymers & aviation fuels, withoptimised costs & zero waste requested by the market

Sustainablenon-edible oils

Lignin,solid residues

Scenarios forbiorefinery

concepts underspecific regional

conditions

Contribution tonew process& biomassproduct

standards

Original

biochemical

conversion

processes

Innovative

catalytic

conversion

processes

Integrated

modular &

flexible

process design

Integrated

modular

bio-

refinery

pilot

plants

Advanced

thermo-

chemical

conversion

processes

Figure 1 - EuroBioref concept

EuroBioRef_p35-37_scm07_EuroBioRef 7/14/10 10:04 AM Page 35


Sustainability


• The variety of available biomass feedstocks,matched with a variety of pre-processing options topre-treat them into viable pre-products, which aresubject to logistical optimisation

• The variety of markets for bio-based products,matched with a variety of integration options tocombine several conversion modules with pre-treat-ed feedstock availability, thus avoiding excessivetransportation of inputs and outputs

• The flexibility of conversion routes, which makes itpossible to integrate key modules with existing facil-ities in order to reduce investment risks

• Proximity to both adapted feedstocks and expect-ed markets, which can be combined with integra-tion into existing or specifically adapted facilities,selecting suitable sites through system analysisThe ‘standard’ biorefinery concepts use massive

economies of scale at one dedicated site to achievehigher performance and optimise along few productlines (e.g. liquid biofuels and electricity, or basic bio-chemicals plus ethanol or biodiesel). These are riskyinvestments, as logistical requirements drasticallyincrease with the size of a single plant and marketdynamics may turn simplistic product output optimi-sation into a dead end.

To avoid these risks, the EuroBioRef approach isdeliberately non-selective in nature. It achieves inte-gration along the whole system, from feedstockthrough conversion to markets, thus taking intoaccount overall logistics, feedstock and productdiversification to reduce risks, and internal integra-tion of multiple conversion routes, which are sub-jected to the regionally available (pre-processed)feedstocks, and the prospective (regional) marketsfor the possible outputs.

The concept thus adapts to regional conditions,integrating with existing infrastructure and minimisesrisks, both for the investors and operators and for thefeedstock suppliers as well as for downstream marketpartners. This chain integration is fundamental to theconcept and can be extended through ‘virtual inte-gration’ along logistical chains to cover larger regions.

The process integration starts with the feedstockoptions, their potential pre-treatment, biochemical,chemical and thermochemical conversion, combina-

tion(s) of them, the use of conversion residues asinputs for other internal or external value chains(such as renewable electricity and syngas produc-tion) and output optimisation with regard to down-stream markets.

This concept makes it possible to widen biorefineryimplementation to the full geographical range ofEurope, adapting to local conditions and resources. Italso offers better opportunities to export biorefinerytechnology ‘packages’ to more local markets and feed-stock ‘hot spots’ in developing countries andeconomies in transition.

Concept principlesThe new proposed concept is based on several princi-ples that must be included in the new biorefinery tobridge the gap between agriculture and the chemicalsindustries by providing a stream for a variety of bio-mass feedstocks and producing a menu of finishedgreen chemical products adapted to the future sus-tainable bio-based European society.

More specifically, biomass raw materials can comefrom a large variety of sources from northern andsouthern Europe but also from other parts of theworld. They can be sourced from agricultural and for-est residues and dedicated non-food crops, which donot compete with food crops in terms of agriculturalland use as they can grow on less fertile fields, with lowwater and fertiliser requirements.

Secondly, integrated biorefinery production shouldbe adapted to such a variety of sustainable biomasssources in the various regional and European contextsby a combination of adapted logistics, flexible process-es and socio-economic viability;

In addition, the diverse biomass sources shouldbe pre-treated efficiently and produce a variety offractions (cellulose, hemi-cellulose, lignin, refinednon-edible oils, seed-meal, glycerine, fattyacids/esters, solid residues, etc.). For these, separa-tion has to be optimised and used in the mostadded-value, eco-efficient and optimised way for theproduction of marketable products.

The development of an original variety of eco-efficient chemical, biochemical and thermochemi-cal routes is the key for the production of mar-ketable high value-added chemicals, biofuels, poly-

mers and materials in a competitive way. An intel-ligent crossroad design can combine these routesin a way that optimises them and uses their by-products.

Moreover, the by-products of the different routeshave to be reintroduced into the integrated process asreactants or energy or even transformed in productsin order to obtain a zero-waste biorefinery. Finally, lifecycle, economic and socio-economic analysis willensure that the whole production chain is optimised ina sustainable way.

The EuroBioRef integrated concept (Figure 1) isthus based on a diversified, flexible and zero wasteapproach. This includes an integrated cluster ofbiotechnological and chemical industries, using a vari-ety of different technologies to produce a wide rangeof valuable commodities and end-products fromdiverse sources of biomass pre-treated raw materials inan eco-efficient way.

Integration aspects will be treated simultaneously,making possible the integration of: different feedstocksto produce the targeted molecules; different transfor-mation pathways to convert biofeedstocks efficiently;of (bio)reactions and separations in order to generatenew efficient processing technologies; and, sustainableand flexible process designs that take socio-economicand regional contexts into consideration. The projectwill develop and then demonstrate at the industrialscale the closer to the market a socio-economic viableprocess of the EuroBioRef biorefinery concept.

ObjectivesThe aim of the EuroBioRef concept is to make possi-ble the large-scale research, testing, optimisation anddemonstration of processes in the production of awide range of products, while using all of the fractionsof the various biomasses and exploiting their potentialto produce the highest added value possible in an eco-efficient and sustainable way.

The project also seeks to overcome the frag-mentation of the efforts of the whole biomassvalue chain, notably land use, agriculture, secondgeneration biomass treatment, thermo- and bio-chemical conversion, new green marketable prod-ucts, bio-aviation fuels, socio-economic sustainabledevelopment.

• CNRS • Alma Consulting Group• UCCS • Arkema

Coordination

• Danish Technological Institute • EUBIA• Imperial College London • Quantis

Sustainability & Economic Viability

Feedstock

Aviation fuels

(Bio-, thermochemical) reactions

Integration &separation

Explanationdissemination &communication

• SoaBE Partners• Danish Technological Institute• Kane Cres• Uniwersytet Warminsko-Mazurski

• WK Rzezów• OBR PR Plock

SSust iaina ibi ility && Econo imicc Viab

Pretreatment

• Borregaard• Novance

• PDC

• TU

• Merck

• CNRS • Umicore • UCCS • SINTEF • Ircelyon • Haldor Topside • Sciences Chimiques de Rennes • Nykomb Synergetics • Universidade do Porto • Metabolic Explorer • Arkema • Novozymes • ISFTA • Orgachim • Merck KG&a • CIRCC• Novance• RWTH Aachen University

• CIRCC

• EUBIA

• Arkema

• ISFTA

• OBR PR Plock

• CNRS

• UCCS

Figure 2 - Implementation of EuroBioRef project execution strategy


Sustainability



It therefore requires greater networking, coordina-tion and cooperation among a large variety of actorsfrom agriculture and the biochemicals and chemicalsindustries, including SMEs, and the scientific biomassknowledge chain, as well as actors from sustainabledevelopment and policy rules advisors.

The new EuroBioRef design will adopt a flexible andmodular process design that should be adaptable inlarge- and small-scale production units for installationin multiple European regions, depending on site-spe-cific biomass resources and needs. The overall effi-ciency of this approach will clearly exceed existingpathways and will consider sustainable options inorder to:

• Produce and use a large diversity of sustainable bio-mass adapted to various European regions but alsofor sustainable development in third countries

• Produce high energy (42 MJ/kg) bio-aviation fuelsthat could replace traditional fuels

• Produce multiple products (chemicals, polymersand materials) in a flexible and optimised way thattakes advantage of the differences in biomass com-ponents and intermediates while maximising thevalue derived from the biomass feedstock

• Improve cost-efficiency by 30% through improvedreaction and separation effectiveness (e.g. reducedseparation and waste disposal costs), reduced capi-tal investments (e.g. novel integrated processes andreactor concepts), improved plant and feedstockflexibility and reduced production time and logistics

• Produce zero waste and rationalise the use of rawmaterials, reducing feedstock consumption by atleast 10%

• Reduce by 30% the energy needed to manufacturethe desired products and operate specific processesusing land more efficiently, using less energy-con-suming reactions and producing the heat andpower needed by the biorefinery

• Reduce time-to-market by 30% by developing newbiorefinery manufacturing processes adapted inparticular regional contexts through intelligent con-ceptual process design methods

EuroBioRef approachThe key challenge for the new biorefinery processdesign is its capacity to apply its potential towardssignificant improvement of total biomass efficiency,which will benefit producers, the environment,industry and end users. This will be obtainedthrough the proposed multi-level integratedapproach, involving a large number of key points(Figure 2).

The first is efficient and adapted biomass pro-duction for Europe and the integration of sustain-able development in Third World countries. Thiscan be achieved by several transition paths,notably improving the efficiency of using existingresidual forms of biomass and sustainableimprovement of the yield and quality of biomasscrops, especially non-food crops.

Also vital is transversal activity to rationalise thewhole process by combining assessments on theoptimisation of crop culture rotation logistics withaspects of the whole biomass value chain, flexibleprocess design and consideration of life cycle analy-sis, socio-economic and policy aspects.

Second generation advanced pretreatment ofbiomass for the sustainable production of lignocel-lulosic materials is also important. This involves thecross-integration of a bio-oil route with a lignocel-lulosic route, which offers original perspectives forcross-valorisation of derived primary products(notably cellulose and oils) including by-products(glycerine and lignin), while in parallel developingoriginal applications inherent to each route.

Enzymatic and catalytic transformations, bothhomogeneous and heterogeneous, will need to beinterwoven. When necessary, they will also have tobe integrated with new separation techniquesand/or reactor technologies.

This must yield a very large variety of productswith - high value-added - niche applications andlarge volume applications, including bio-aviationfuels, chemicals, solvents and others that must bekept confidential for the moment. These must either

have very fast access to the market, because theyare substituting homologous petrochemical-derivedproducts, or be very innovative, with high potentialfor larger downstream developments.

The technical and economic feasibility and effi-ciency of the different steps and building blocks, aswell as of the majority of applications and some sub-processes, will be demonstrated in pilot plants andthe units will work either in a centralised or a decen-tralised way. This will ensure design flexibility, adapt-ing the most rational system to each local and glob-al economical constraint.

Zero waste will be generated by several means:the implementation of applications for each type ofby-products with reutilisation in the global loop;implicitly, by optimising the catalytic processes foratom and energy economies; applying green sol-vents in purification processes; converting the mostrefractory by-products via new technologies; and,converting waste to energy.

Finally, the project involves setting up new defini-tions for product quality, taking into account the bio-mass-issued product specificity that are thus specifi-cally suitable for biorefinery-dictated applications.Quality by design, in other words.

*Acknowledgements: This project is funded by the EU 7th FrameworkProgramme (FP7/2007-2013) under grant agreement 241718EuroBioRef

For more information, please contact:Franck DumeignilUnité de Catalyse et de Chimie du Solide -UMR CNRS 8181Univ. Lille Nord de FranceUniversité Lille 1, Sciences et TechnologiesBâtiment C3Boulevard LangevinF-59655 Villeneuve d’Ascq CedexTel: +33 3 20 43 45 38 E-mail: [email protected]: http://eurobioref.org/

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James Thomson of Ceimig looks at the chemistry of the heaviest of the metallic elements

Osmium chemistry

In 1803, Smithson Tennant (1761-1815) wrote“fusion with alkali of the black residue remain-ing after treatment of native platinum with

aqua regia followed by extraction and acidificationof the melt gave a pungent and peculiar smell ...from the extrication of a very volatile metal oxide,and, as this smell is one of its most distinguishingcharacters, I should on that account incline to callthis metal Osmium”.1

This moment in the history of chemical discoveryrecorded the first transaction of one of the mostmysterious elements of the periodic table. From thecolour of the metal sponge being an impressiveblue, its high density, its ability to form one of thehighest oxidation states of all the metals - onlyruthenium and osmium give VIII oxidation states -the high volatility and toxicity of osmium tetroxide,all give this metal a unique mystique. This articlewill review some of the chemical properties andapplications of this element and hopefully invigor-ate researchers to the interesting world of osmiumchemistry.

The principle oxidation states of osmium are 0,II, III, IV, VI, and VIII. Its density is 4.906 g/cm-3,its melting point is 40.6˚C and its boiling point is130˚C. Osmium is known to achieve the (VIII) oxi-dation state with dioxygen and difluorine, the (IV)oxidation state with fluorine or iodine and the (III)oxidation state with chlorine. It is tervalent withnitrate and can form the zero oxidation complexwith carbon monoxide. The atomic packing inosmium metal is hexagonal. Osmium metal meltsat 2,700˚C.

Osmium tetroxide in the aqueous phaseThe reaction of dioxygen with osmium sponge at550˚C yields a yellow condensate at 40˚C, whichsubsequently solidifies to a transparent crystallinesolid crop. This lemon yellow solid is broken up anddispensed in vials of varying quantities that users ofosmium (VIII) oxide would immediately recognise.

Osmium (VIII) oxide is volatile (7 torr at stan-dard temperature and pressure (STP)) and toxic; itattacs the eyes, irritates the olfactory glands andinduces bronchial conditions. It has a pungentchlorine-like smell, hence the vapours are easilydetected and accidents are rare. Washing withcopious quantities of water usually expunges anycontamination.

Osmium tetroxide (OsO4) is moderately solublein water, giving a yellow solution, this colour beingconsistent with the osmium (VIII) oxide structurebeing tetrahedral. The solubility at STP of crystallineOsO4 in water is limited, at 7.2 wt%. Solutions areusually supplied commercially as 2 or 4 wt% but canbe anything up to around 6 wt%.

Owing to the low solubility of OsO4 in water, itis sometimes more convenient to generate it insitu. This is achieved by using potassium osmate(K2[OsO4(OH)2]). In strong alkaline solutions, theyellow colour of OsO4 gives a deep red solutionfrom which red K2[OsO4(OH)2] is formed. This isa convenient material to give osmium (VIII) oxide,in which the solvated anion undergoes an acid-catalysed dehydration step to form OsO4 in situ:

2K2[OsO4(OH)2] + 4H+ ÷ 2H2OsO4 + 4KOH ÷OsO2 + OsO4 + 4KOH + 4H2O

The OsO4 thus generated is then available toundergo a typical Sharpless osmylation (Figure 1).4,5

Cis-hydroxylation of π-bondsA valuable use of OsO4 solution is the oxidation ofolefinic bonds. The reaction is highly selective, giv-ing cis-hydroxylation of the π-bond to yield gly-cols. The demand from the pharmaceuticals andagrochemicals industries for chiral 1,2-diolsrequires a suitable oxidative catalyst.

The formation of 1,2-diols by OsO4 has beenextensively studied.6,7 It is unsurpassed in its abil-ity to catalyse syn-diols from alkenes.4,5 The kinet-ic rate for the cis-hydroxylation reaction is acceler-ated when olefins contain a sterically strained π-bond.2,8,9 For the Sharpless osmylation reaction,the osmium centre initiates asymmetric dihydrox-ylation by modifying itself through the formationof a cyclic diolate.4 Basically, the mechanism isconsistent with the addition of O=Os=O to theC=C bond.2

The hydroxylation reaction of olefins is catalyticwhen OsO4 is used in the presence of hydrogenperoxide or perchlorate ion. The oxidation of olefinsto 1,2-diols is by a two step sequence: epoxidationof an olefin followed by peroxide or peracid, thenhydrolysis of the resulting peroxide.10

The osmium-catalysed route to 1,2-diols is themost efficient, reliable and atom-efficient method.

OsO4 is used to hydroxylate the olefin to the diolcatalytically in the presence of a secondary oxi-dant (e.g. hydrogen peroxide).

Studies of the reaction as a function of pH haveshown that the oxidative reaction is better per-formed in acidic solutions and citric acid performswell as a suitable pH buffer. Recent work has alsoshown that the addition of co-catalysts such as N-methylmorpholine (NMO) together with flavinmarkedly improves the re-oxidative properties,promoting OsVI back to OsVIII by the hydrogenperoxide-catalysed OsO4.11

Using ligands such as hydroquinidine 1,4-phthalazinediyl di [(DHQD)2PHAL] in conjunctionwith NMO/K3[Fe(CN)6] has demonstrated ee val-ues of about 94-96” for asymmetric diolation reac-tions. These chiral cinchonidyl ligands have alsobeen used in the heterogenisation of osmylationchemistry.

Osmium (VIII) tetroxide & other solventsOsO4 is sparingly soluble in water (about 6.47 gmin 100 gm of 18.2 M ohm/cm3) yet very solublein carbon tetrachloride (about 250 gm in 100 gmof CCl4 at 20˚C). As mentioned, this aqueous sys-tem is used in the dihydroxylation of olefins. Thecis-hydroxylation of olefins is reported to be fasterin the presence of pyridine as the solvent.12

When OsO4 is heated to 175˚C in xylenetogether with carbon monoxide at 190 bar in anautoclave, dodecacarbonyl tris-osmium(Os3(CO)12) is produced.13 This reaction in xylenegiving Os3(CO)12 reacts in situ with triphenylphos-phine and is a convenient route totris[Os(CO)3(PPh3)].14

Supercritical CO2 has been used for the dihy-droxylation of olefins in the presence of ionic liq-uids.15 This procedure was used to prepare chiralvicinal diols as precursors for biological active inter-mediates and ee’s of 90-97 were achieved using N-methylmorpholine oxide as a co-oxidant with potas-sium osmate for the asymmetric diolation of 1-hex-ene.

This procedure also used cinchonyl ligands toinduce enantioselectivity into the products. Chiralmodifiers such as hydroquinidine 1,4-phtha-lazinediyl (DHQD)2PYR, (DHQD)2PHAL,(DHQD)2AQN and (DHQD)2PHAL gave high eevalues in conjunction with osmium (VIII) oxide.16

Microencapsulation of OsO4The high toxicity associated with OsO4 in con-junction with its volatility is particularly importantfor its use in large-scale processes - hence thedevelopment of a microencapsulation route usingan insoluble polymer-supported osmylate beads,together with a suitable solvent.17

This procedure involves the immobilisation ofOsO4 onto a polystyrene-based polymer. When


Reactions & scope of osmium chem

R1 R2

R4R3

2OsO4

O

O

O

OO O

O

OR1R2

R3 R4

R2R1

R3R4

ClO3-

H2O2OsO4

R1 OHR2

OHR3R4

2 x+2 x

Figure 1 - Osmylation through a Sharpless addition mechanism

Ceimig_p38-40_scm07_Ceimig 7/14/10 10:08 AM Page 38


Osmium chemistry

this was done in conjunction with NMO, the dihy-droxylation of cyclohexene was achievable. TheOsO4-polymer was recovered by filtration andreused for five cycles without significant degrada-tion to the kinetic turnover frequency.

Subsequently an acrylonitrile/butadiene/poly-styrene polymer was used as the microcapsulationmedium and (DHQD)2 PHAL as the chiral pro-moter gave an ee of about 95.18 The microencap-sulation of osmium (VIII) tetroxide in polyureabeads has demonstrated good success in the dio-lation of α-methylstyrene.15

The encapsulated OsO4 in conjunction withNMO gave yields of about 80-90% in the diola-tion of α-methylstyrene and styrene derivatives.Asymmetric diolation of α-methylstyrene in thepresence of (DHQD)2PHAL also gave a yield of97% with an ee of 94.

Biochemistry applicationsOsmium (VIII) oxide as a 2 wt% solution or invapour form is used for fixing and staining celland biological tissue for use in microscopy andelectron microscopy studies. The fixation of cellsby osmium (VIII) tetroxide is a non-destructivemethod to lock the cellular organisation of the bio-logical material.

The staining method involves the pre-treatmentof the biological material with a suitable aldehydefollowed by immersing the treated material in 2wt% OsO4 solution. Alternatively the biologicalmay be exposed to the vapours of osmium tetrox-ide followed by washing, staining, embedding thebiological material in resin and slicing, followed bymicroscopy examination. The staining processinvolves attacking the lipid and unsaturated bondscontained in the lipid material, forming osmate(VI) esters and/or dioxo bridges.9

Osmium (VIII) oxide is also used in glucosesensing. During the late 1980s, the developmentof mediator-coated electrodes led to an ampero-metric approach to the determination of concen-trations of glucose in biological fluids.

The sensor measures the transfer of electronsbetween the enzyme and the electrode throughthe use of a multivalent co-ordination complexknown as a mediator. Fluoranil, chloroanil, polyvi-ologen and ferrocene are common and availablemediator complexes. The efficiency and speed ofglucose sensing depends on the mediator used.

Co-ordination complexes of transition metalcations, usually iron, ruthenium or vanadium, areused as the variable reduction/oxidation electroncentres. Some of the mediators are volatile, pho-toactive, reactive to molecular oxygen and subjectto hydrolysis, such as ferrocene. The photoactivityand hydrolytic nature of ferrocene results in thedegradation of the material, so suitable storagecriterion are a pre-requisite for long term use.

Osmium-bis-N,N’-(2,2’bipyridyl-N-(pyridine-4-yl-methyl-(6-pyrrole-1-yl-hexyl)amine dichloride

and analogous osmium-pyridyl complexes havebeen shown to be suitable electron transferreagents in oxygen insensitive glucose biosen-sors.19 The bipy osmium complex is preparedfrom potassium hexachloroosmate and theentrapped electron induces a glucose dehydroge-nase reaction.

Tris(4,4’-dihydroxy-2,2’bipyridine) osmium(Figure 2a) is chemically stable, yet reactive to glu-cosase reduction. It gives an electrode response of+150 mV (at pH 1, calomel reference electrode)and -1V at pH 13. Investigations have led to thepreparation of (4-4’-dimethoxy-2,2’bipyrydine)(Figure 2b), while bis(4,4’-dimethyl 2,2’bipyridine)derivatives of osmium have been used as media-tors, resulting in good glucosase potential.

Electronic applicationsOsmium (II) complexes have been shown to beefficient organic light-emitting diodes (OLEDs).20

Chelating 3-(trifluoromethyl)-5-(2-pyridyl)pyrazoleor the corresponding 3-(tert-butyl triazole) withthe osmium (II) cation in the equatorial positionsand phosphine donors at the axial locations bal-ances the overall charge on the molecule.

Recently, phosphine ligation has been replacedwith methyl diphenyl phosphine and the resultsshow high luminescence properties in methylenechloride at λmax values of 617, 632 and 649 nm.This osmium (II) phosphor is a red emitter and hasreceived intensive study.21-23

The preparation of these red-emitting OLEDs fol-lowed the preparative methods described for theblue-emitting carbonyl analogues, 3-trifluoromethyl-5-(2-pyridyl)pyrazole or 3-tert-butyl triazole osmium(II) dicarbonyl. These blue emitters have the car-bonyl ligands in an axial and equatorial positionrespectively of the octahedral structure.24

The λmax for the carbonyl osmium complexesdescribed is about 340 nm and this is attributedto the MLCT properties of the complex. Thesecarbonyl osmium (II) OLEDs show a depreciation

in the activity of the OLED as a function of time,owing to the cationic nature of the molecularstructure.

The loss in activity has been attributed to a lowenergy bonding between the osmium (II) centreand the counterions within the crystalline matrix -hence the synthesis of the phosphor analogueswhere the osmium (II) phosphor complex is in aneutral charge state. This neutral charge over themolecule appears to stabilise the phosphor fromdeactivation.21

These studies show that the emission spectrafrom carbonyl osmium complexes are sensitive tothe coordination ligands associated with the axialor equatorial positions of the osmium octahedra.This work offers great interest in the study ofOLED devices and the structural coordinationchemistry of carbonyl osmium complexes.

Homogeneous catalysisK2[OsO4(OH)2]-catalysed reactions with phtha-lazine ligands have proved surprisingly efficient inthe preparation of ee’s of >90 in olefinic dihy-droxylation.5 A mixture of K2[OsO4(OH)2], potas-sium ferricyanide and potassium carbonate wasmixed with 1,4 bis-(9-O-dihydroquinidinyl)phtha-lazine [(DHQD)2PHAL] or 1,4 bis-(9-O-dihydro-quininyl)phthalazine [(DHQ)2PHAL].15 The OsO4

shows an ability to turn over 400 olefin mole-cules/OsO4 to give extremely high ee values.

Osmium co-ordination compounds have founduses in hydride shift catalysis by phosphorus co-ordination complexes.17 Phosphino-chelatedhydridocarbonyl osmium (I I) complexes likeOsHCl(CO)(PPh3)(Ph2P(CH2)n {n=1-3} have beeninvestigated with respect to the hydrogenation oftrans-cinnamaldehyde using isopropanol as thehydrogen donor.

These co-ordination complexes of osmium havealso been shown to be active by a pseudo-firstorder rate law in the homogeneous hydrogena-tion of propionaldehyde to propan-1-ol in tolueneat 110˚C under 20 bar dihydrogen.

Comparative analysis of ligand effects haveshown PPh2PFe(C5H4-η5)2PPh > PPh2P(CH2)3PPh2

> Ph2PCH=CHPPh2 >Ph2P(CH2)PPh2 >Ph2P(CH2)2PPh2. The results indicate that the pres-ence of the chelating ring results in a higher catalyt-ic performance than the carbonyl complexOsHCl(CO)(PPh3)3.

Applications are also found in nitrogen co-ordi-nation. In aqueous solutions with pH of >8, macro-cyclic amine complexes of osmium (trans-[OsVI-1,4,8,11-tetra-methyl-1,4,8,11-tetraazacyclotetrade-cane)O2]2+ undergo a reversible one-electronreduction to osmium (trans-[OsV-1,4,8,11-tetra-methyl-1,4,8,11-tetraazacyclotetradecane)O2]2+.

In acidic solutions the electrochemical reductionof osmium (trans-[OsVI-1,4,8,11-tetra-methyl-1,4,8,11-tetraazacyclotetradecane)O2]2+ is areversible three-electron three-proton transfer


m chemistry: An overview

N

N

OH

OH

OsL2

L4L3

L1

N

N

OCH3

OCH3

OsL2

L4L3

L1

Figure 2 - 4,4’-dihydroxy-2,2’-bipyridine (a) &4,4’-dimethoxy-2,2’bipyridine (b)


Osmium chemistry



process.25 These amine complexes of osmiumseem inert to ligand exchange processes.

Heterogeneous catalysisJacobs made the first reports of a heterogeneousdiolation reaction, describing what was effectively areversed heterogeneous catalysis procedure.17 Thegroup immobilised a tetraolefin to a silica supportvia covalent bonds. This heterogeneous phase wasthen reacted with OsO4 solution to give a osmyldiolate ester that is hence fixed to the silica support.

The catalytic process then takes place at the co-ordinatively unsaturated osmium tenvironments.Next, the group demonstrated the feasibility of

this procedure by the diolation of mono and dis-ubstitution of aromatic olefins using NMO as theco-oxidant.

Choudary developed this approach by design-ing an ion-exchange column where the osmiumwas immobilised onto silica supported on anorganic resin.26 The work demonstrated the asym-metric dihydroxylation of trans-stilbene with an eeof about 96%, in which the reactivity was superi-or to that of a potassium osmate benchmark.Choudary prepared a silica gel-supported titaniumsilicate phase, upon which (DHQD)2PHAL-OsO4

reacted with an appropriate alkaloid. NMO wasused as the co-oxidant.27

Immobilisation of the reactant has also been shownto give good results for the asymmetric aminohy-droxylation of olefins.28 This approach also anchorsthe ligand onto an insoluble polymer (PEG) to whichcinchona-derived alkaloids, 1,4 bis-(9-O-dihydroquini-dinyl)phthalazine [(DHQD)2PHAL] or 1,4 bis-(9-O-dihydroquininyl)phthalazine [(DHQ)2PHAL], werebonded, where N-chlorocarbamate was used underSharpless reaction conditions. The reaction gives β-amino alcohols with high ee values.

*Also contributing were M.J. Duncan & C.A. McGowan, also ofCeimig. The author would like to thank colleagues at Ceimig fortheir respective support and assistance in the preparation of a widerange of osmium complexes and in particular the preparation ofosmium (VIII) oxide crystal.

References:1. Smithson Tennant, Phil. Trans. 1804, 94,4112. W.P. Griffiths, Platinum Metals, Rev. 1974,18, 94-963. D. McDonald, Platinum Metals Rev. 1961,5, 1464. S.G. Henteges & K.B. Sharpless, J. Am.Chem. Soc. 1980, 120, 42635. K.B. Sharpless, W. Amberg, Y.L Bennami,G.A. Crispino, J. Hartung, K.-S. Jeong, H.-L.Kwong, K.Morikawa, Z.-M. Wang, D. Xu & X-L. Zang, J. Org. Chem. 1992, 57, 27686. P.N. Rylander, Engelhard Ind. Tech. Bull.1968, 68, 907. F.R. Gunstone, Adv. Org. Chem. 1960, 1,103

8. Z.-M. Whang, H.C. Kobb & K.B. Sharpless,J. Org. Chem. 1994, 59, 51049. R.J. Collin, W.P. Griffith, F .Philips & A.C.Skapski, Biochim. Biophys. Acta. 1973, 320,74510. N.A. Milas & S. Sussmann, J. Am. Chem.Soc. 1936, 58, 130211. V. Van Rheenen, R.C. Kelly & D.F. Cha.,Tetrahedron Lett. 1976, 197312. R. Criege, B. Marchand & H.Wannowius, Ann. 1942, 550, 9913. B.F. Johnson, J. Lewis, I.G. Williams & J.Wilson, Chem Commun. 1966, 39114. C.W. Bradford, Platinum Metals Rev.1967, 11(3), 10415. L.C. Branco, A. Serbanovic, P.M.Numesda & C.A.M. Alonso, Chem. Commun.

2005, 10716. K.L. Reddy, K.R. Dress & K.B. Sharpless,Tetrahedron Lett. 1998, 39, 36617. A.Severyns, D.E. DeVos, L. Fiermans, F.Verpoort, P.J. Grobet & P.A. Jacobs, Angew.Chem. 2001, 113, 60618. M.A. Anderson, R. Epple, V.V. Foki & K.B.Sharpless, Angew. Chem. 2002, 114, 49019. R.J. Foster & F.E. Keyes, Phy. Chem.Chem. Phys. 2001, 3, 133620. Y.L. Tung, P.C. Wu, C.S.Liu, Y.Chi, J.K.Yu,Y.H. Hu, P.T. Chou, S.M. Peng, G.H. Lee, Y.Tao, A.J. Carty, C.F. Shuand & F.I. Wu,Organometallics 2003, 23, 374521. B. Carlson, G.D. Phelan, W. Kaminsky,L.Dalton, X.Z.S.L Jaing & A.K.-Y. Jen, J. Am.Chem. Soc. 2002, 124, 14162

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July 25-30 Chemistry & Biology of Salve Regina University, Diane McLaughlin, Email: [email protected] - conference North Carolina, Gordon Research Website: www.grc.org

US Conferences, US

July 25-30 Green Chemistry - conference Davidson College, Diane McLaughlin, Email: [email protected] Carolina, Gordon Research Website: www.grc.orgUS Conferences, US

July 28-31 4th Dye + Chem Bangladesh Bangabandhu International CEMS, Tel: +880 2 8812713Expo - exhibition Conference Centre, Bangladesh Email: [email protected]

Dhaka, Bangladesh

August 1-6 Solid State Chemistry Colby-Sawyer College, Diane McLaughlin, Email: [email protected] - conference North Carolina, Gordon Research, Website: www.grc.org

US Conferences, US

August 1-6 11th International Conference University of Oulu, Professor Risto Laitinen, Tel: +358 8 553 1611on the Chemistry of Selenium Finland University of Oulu, Email: [email protected]& Tellurium (ICCST-11) Finland Website: www.oulu.fi

August 1-6 18th International Conference Bergen, Professor Leiv Sydnes, Tel: +47 55 58 3450on Organic Synthesis Norway University of Bergen, Email: [email protected]

Norway Website: www.iupac.org/web/act/bergen

August 2-6 Advances in Emulsion Hotel Belvedere, Dr F. Joseph Schork, Tel: +1 301 405 1074Polymerisation & Latex Davos, University of Maryland, Email: [email protected] - short course Switzerland US Website: www.davoscourse.com

August 8-13 Medicinal Chemistry Colby-Sawyer College, Diane McLaughlin, Email: [email protected] conference North Carolina, Gordon Research Website: www.grc.org

US Conferences, US

August 15-19 3rd IUPAC Conference on Ottawa, Professor Philip Jessop, Tel: +1 613 533 3212Green Chemistry Canada Queen’s University, Email: [email protected]

Canada Website: www.iupac.org/web/act/ottawa

August 17-19 CPhI South America 2010/ICSE La Rural - Hall Ocre, Martin Wilson, Tel: +31 346 559444South America 2010/P-Mec Buenos Aires, CMP Information, Email: [email protected] America 2010/BioPh South Argentina Netherlands Website: www.cphi-sa.comAmerica 2010 - exhibitions

August 23-24 Informex Latin America 2010 Amcham Convention Luciana Rose, Tel: +11 4689 1935- exhibition Centre, UBM, Email: [email protected]

Sao Paulo Brazil Website: www.informexlatam.com.br

September 5-9 19th International Conference Vienna, Tatiana Zamulina, Tel: +7 383 326 9536on Chemical Reactors Austria Boreskov Institute Email: [email protected]

of Catalysis, Russia Website: http://conf.nsc.ru

September 7-10 2nd Asia-Pacific Conference on Dalian Bayshore Hotel, Cuiling Lan, Tel: +86 10 6859 7750Ionic Liquids & Green Processes China Centre of International Email: [email protected]

Scientific Exchanges, Website: www.apcil.orgChina

September 8-9 Chemical Industries Cité Centre de Congrês, Informa Life Sciences, Tel: +44 20 7017 7481Regulations - conferences Lyon, UK Email: [email protected]

France Website: www.informa-ls.com/cirSeptember 10-15 Solid State Chemistry 2010 Prague, Institute of Inorganic Tel: +420 266 173 113

- conference Czech Republic Chemistry, Email: [email protected] Republic Website: www.ssc2010.cz

September 13-15 Organic Process Research Barcelona, Scientific Update, Tel: +44 1435 873062 & Development - conference Spain UK Email: [email protected]

Website: www.scientificupdate.co.uk

September 13-15 Orchem 2010 - conference Weimar, GVK, Tel: +49 69 7917-0Germany Germany Email: [email protected]

Website: www.gdch.de

September 14-16 PharmaChem Outsourcing Ocean Place Resort, Mark Alexay, Email: [email protected] - conference & exhibition Long Branch, PharmaChem Outsourcing, Website: www.chemoutsourcing.com

New Jersey, USUS

September 15-19 10th International Chemical Shanghai New International Sarah Chen, Tel: +86 10 6422 2898Industry Fair (ICIF) China Expo Centre, CCPIT Sub-Council of Email: [email protected]

China Chemical Industry, China Website: www.icif.org.cn

September 20-23 26th Congress of the IFSCC Buenos Aires, Society of Cosmetic Tel: +44 1582 726661 Argentina Scientists, Email: [email protected]

UK Website: www.ifscc2010.com

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