13015644 speciality chemicals oct2008[1]

Dual actionChirality in cosmetics

The rightformulaDistributors or formulators?

Dual actionChirality in cosmetics

The rightformulaDistributors or formulators?

www.specchemonline.com

Agrochemical intermediates ... Watertreatment chemicals ... Halo-organics

Magazine

Also:

... and all the latest news

OCTOBER 2008 Volume 28 No. 08

Front_cover.qxp 7/10/08 12:11

From Organic Intermediates to Biochemicals, from Performance Chemicals to Food Ingredients, Camida can source, manage and deliver your needs.

Whether your business is in pharmaceuticals, food, biotechnology or surface coatings, we meet the highest industry standards and conform to the most stringent international protocols.

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Project1 7/10/08 12:21 Page 1

Volume 28 No. 08

RegularsEditor’s letter 4

News 6

Forthcoming events 46

Agrochemical intermediatesA quiet giant 12Weylchem has quietly emerged as a major player in agrochemical custommanufacturing. Andrew Warmington spoke with joint managing directorGeorg Weichselbaumer

Non-crop pesticides on the move 16Rod Parker of Agricultural Information Services highlights remarkable developments in the non-crop business for pesticides and argues that we are likely to see more of this

Me too - but what to do? 18Nicola Mitchell of Life Scientific offers a guide to the EU registration of generic plant protection products

Water treatment chemicalsChemicals & the future of water 20Dr Elizabeth Milsom outlines the Royal Society of Chemistry’s recent report on sustainable water

The whole package 24Chemicals are increasingly part of wider water treatment systems. Sean Milmo reports

IDA resins: Versatile specialists 26Dr Stefan Neumann of Lanxess looks at a selective ion exchanger for handling heavy metals

Cosmetics & personal careA different formula 28Distributors play a role that goes way beyond simple distribution in the personal care industry. Ahead of SCS Formulate, we interviewed some of the key UK players

Chirality - a cosmetic concern? 32Some claim that ‘chirally pure’ cosmetic products are more effective. Dr Cynthia Challener investigates

A novel low-temperature extraction of botanicals 36Dr Charles Scanio and Patrick McFadden of Naturel Extracts describe a new botanical extraction process

Halo-organicsNew perspectives on difluorination technology 38Dr Yasushi Matsumura of Asahi Glass introduces new difluorination techniques for APIs and intermediates

Easy-clean or super easy-clean 42Steven Block of Dow Corning and Salvatore Re of Daikin Chemicals Europe report on the development of new generations of surface modifiers

Speciality Chemicals Magazine October 2008 3


24Tapping into wholesystems

18Wheat from the chaff

In the next issues of Speciality ChemicalsMagazine

November• Biotechnology• Flame retardants• Leather & textilechemicals• Organosulphurchemistry

December• Outsourcing• Contract research &toxicology• Oilfield chemicals• Peptides & proteins • Informex USA 2009preview

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Contents.qxp 7/10/08 12:11

Well, that was quick, wasn’t it? In the blink of an eye, all

of the investment banks have gone from Wall Street.

OK, that is not the least of what has been happening

and the model had already changed, but the point still stands.

From five giants at the start of the year, there are none.

No-one, to the best of my knowledge, seriously claims to have

seen this coming, as Bear Stearns, Lehman Brothers and Merrill

Lynch went down one by one. Within a few days, though,

Morgan Stanley and Goldman Sachs, who seemed to have the

wherewithal to withstand the fiercest financial storms, hastily

changed themselves purely to survive.

There is an element of schadenfreude for a cynical left-winger

like me in seeing the banking sector hoist by its own petard. A

time-honoured business model has been hastily murdered

because the herd mentality has turned against it, but this time it

is members of the herd - albeit not necessarily the most guilty

members - who have lost their jobs. (And AIG received their just

desserts for sponsoring Manchester United, ha ha.)

The trouble is that more deserving industries, like chemicals,

are no less vulnerable than they were before to the vicissitudes of

the financial markets. All of which brings me, in a roundabout

way, to what this all means for fine and speciality chemicals,

where there is a clear consolidation trend at the moment.

There is no doubt that times are tough in speciality chemicals

and that this is driving rapid change. For examle, Plimsoll recent-

ly estimated that 55 of 210 speciality chemicals firms in the UK

are losing money. “Companies are faced with a stark choice: hold

on to sales at reduced margins or opt to reduce in size of scale,”

Plimsoll warned.

From Switzerland, Kaffenberg & Partner and Helbling

Corporate Finance, M&A consultants who deal exclusively with

speciality chemicals, forecast a continuation in 2008 of last year’s

growing volume of transactions increase. This, they said, reflects

a combination of the growing importance of Asia to the industry,

the increased commoditisation of many speciality products and

the growing power of large customers - factors cited by many

other observers, alongside a desire for forward integration among

commodity players. As a result, European speciality chemicals

companies’ margins have eroded making new strategic

approaches vital; it is ‘grow or go’.

This is clearly happening already. In August, Dow Chemical

agreed to acquire Rohm and Haas, while Ashland and Hercules

agreed a merger. Now, in Europe, Ciba Specialty Chemicals has

accepted a friendly offer from BASF which very few doubt will go

through (page 6). Private equity is still in the market but cannot

realistically outbid a cash-heavy industry player.

So what next? When something happens to Ciba or Clariant,

it is an unwritten law that attention will immediately turn to the

other. Somehow this appeals to the lazy streak in journalists and

analysts. After all, they are both Swiss-based, emerged out of the

break-up of much larger conglomerates, inhabit many of the

same markets and have both been through difficult times in

recent years as end use markets turn down and the high Swiss

franc wipes out any cost-cutting gains.

Add to that the coincidence that, just as Clariant replaced a mar-

keting-minded CEO with one whose experience is in corporate

restructuring, activist shareholders started agitating for the removal

of Ciba chairman Armin Meyer, and the parallels are irresistible.

Then, when Ciba is taken over, the talk becomes deafening.

(In a situation like this, last month’s speculation soon becomes

worthless. Before BASF came into the frame, the possibility of a

merger between Ciba and Clariant was mooted again - some-

thing that was announced then abandoned a decade ago, only

to be resuscitated for gossip almost every other year since.)

So, inevitably, a lot of attention has focused on Clariant - long-

rumoured to be a takeover target for Lanxess - and that is under-

standable in itself. However, on the day BASF and Ciba made

their announcement, the Financial Times’s Lex column cheerfully

pronounced the independent days of both Clariant and Lanxess

numbered. Others have put Chemtura (which recently failed to

find a buyer on acceptable terms), Rhodia, Rockwood Holdings

and Altana in the frame. On what basis is hard to say. Lumping

together these six companies, whose recent results have ranged

from very good to very poor, is simplistic at best. Being active in

speciality chemicals is all that they have in common.

This partly reflects the difficulty of defining what speciality

chemicals are. Every definition varies and there is no definitive

anwer to what the industry is. I remember one chart in the

Financial Times (yes, them again) of the top ten speciality chemi-

cals firms in the world. It was number seven before I saw the

name that I would personally have put number one - Evonik -

and ahead of it were others from agrochemicals, coatings and

other fields. That is not to say I am right and the FT is wrong, but

an industry that is hard to define will always struggle to get the

attention of those whose perceptions of it matter so much.

Does speculation matter? After all, most of it doesn’t come

true. I think the answer is that it matters as much as we think it

does. In these topsy-turvy times, we cling to those who appear

to make sense of the chaos. Financial analysts dislike difficult-to-

define markets. And a combination of this, the herd mentality and

a jittery world financial situation means that the speciality chemi-

cals industry is being put in danger of pushing through restruc-

turing in ways not necessarily driven by the industrial logic that

has prevailed so far.

The integrated speciality chemicals model must change, but it

should no more be swept aside than the investment bank model

should have been. It would be tragic if the industry were to be

driven by the demons others are trying to put into its head, not

least because it actually has more financial muscle than it had a

month ago with which to stand up for itself.

Dr Andrew Warmington

Editor - Speciality Chemicals Magazine

Editor’s letter

Reaping the whirlwindIs merger mania in speciality chemicals necessary for progress or just the latest fad?

“The integratedspecialitychemicals modelmust change, butit should no morebe swept asidethan theinvestment bankmodel shouldhave been.”


4 October 2008 Speciality Chemicals Magazine

Editors_letter.qxp 7/10/08 12:12

Project1 7/10/08 12:23 Page 1

GERMANY/SWTIZERLAND

BASF has agreed to acquire the whole

of the share capital of Ciba Specialty

Chemicals for €2.1 billion, in yet

another of the mega-deals sweeping

across the speciality chemicals sector

this summer. With financial liabilities

and pension obligations factored in,

this gives Ciba a total enterprise value

of €3.4 billion.

The two firms combined currently

have 160 sites, 108,000 employees

and sales of nearly €62 billion/year.

Dr Jürgen Hambrecht, chairman of

the board of executive directors at

BASF said that the ongoing consoli-

dation process in the chemicals

industry must accelerate and that

BASF must play a proactive role in it.

“With the acquisition of Ciba, we

are strengthening our portfolio and

expanding our leading position in

speciality chemicals with products

and services for a variety of customer

industries,” Hambrecht commented.

“We will grow profitably in accor-

dance with our clear and successful

strategy. The transaction meets our

acquisition criteria.”

With Ciba on board, BASF will rise

from forth place to become the top

supplier to the paper chemicals sector

with the broadest product portfolio.

Hambrecht added that this sector is

in particularly urgent need of restruc-

turing and the economies of scale

available through the merger would

help to start this process.

It was paper chemicals above all

that contributed to Ciba’s weak 1H

results (SCM, September 2008, page

8). The company took a net corporate

loss of €353 million on sales that

were 6.6% down to €1,916 million.

This was largely because of a non-

cash goodwill impairment of €369

million it had to take for the Water &

Paper Treatment segment.

BASF will also become world num-

ber two in coating effect materials,

gaining a wider range of pigments,

resins and additives, and will signifi-

cantly boost its presence in plastics

additives, notably in UV stabilisers and

antioxidants; it had hitherto also

ranked fourth in both fields. In addi-

tion, it will also a stronger position in

the automotive, packaging, construc-

tion, electronics and water purification

sectors and in some emerging markets.

Hambrecht confirmed that Ciba’s

home town of Basel will remain an

important site for parts of the com-

bined business, especially research,

and that it will establish a global

operating division there. However,

BASF will accelerate Ciba’s existing

plans for restructuring, which are

scheduled to lead to some 2,500 job

cuts by the end of 2009.

Dr Armin Meyer, chairman of the

board of directors of Ciba, comment-

ed that the deal “combines a fair

price with an industrially compelling

solution for Ciba”. The board had

commissioned an independent fair-

ness option from Perella Weinberg

Partners UK and, on that basis, has

recommended the offer to its share-

holders.

“We are in between the big raw

materials suppliers and the big cus-

tomers. This ‘sandwich position’ is

getting worse and worse,” Meyer

added. Increasing raw material and

energy prices had made its position

increasingly uncomfortable, culmi-

nating in a very weak performance

in 1H.

BASF, Meyer pointed out, is both a

long-standing customer and supplier

to Ciba in many fields, especially in

plastics, coatings and paper. Ciba will

gain wider markets and sources of

supply in such niches as oilfield and

mining chemicals through BASF’s

backward integration into important

raw materials and intermediates, as

well as benefitting from its global

research, production and marketing

platform.

Ciba’s last acquisition before the

deal with BASF was the photoinitia-

tor business of Italy’s Lamperti. This,

the company said, will strengthen its

range of UV curing systems for coat-

ings, inks, adhesives and electronics

and expand its range of photoinitia-

tors suitable for food packaging.

Previously, it had also agreed a joint

venture with Astra Polymer to pro-

duce customer-speficic blends of

antioxidants in the Persian Gulf

region.

BASF’s offer began formally on 1

October and runs until 28 October.

Finance for it is already in place.

Completion is subject to a special

meeting of Ciba shareholders agree-

ing to remove restrictions on the

exercise of voting rights and then

acceptance of the offer by two thirds

of the shareholders. The two firms

expect to complete it no later than

Q1 2009.

BASF may have a battle on its

hands to convince enough Ciba

shareholders, however. Spanish fund

manager, Bestinver, which holds

13.2% of Ciba has already rejected

the offer as too low, while Golden

Peaks, the activist hedge fund with a

1% stake which had been agitating for

Meyer’s removal, is also opposed.

Analyst opinion is that a counter-

bid is unlikely and that the deal will

probably go through, given that BASF

has made a friendly bid, is the largest

chemicals company in the world and

has the highest credit rating among

European chemicals companies.

However, as BASF has said that it

could spend up to €10 billion on

acquisitions, some may try to flush

out a higher price.

BASF could soon add to its war

chest with the sale of its styrenics

activities. It has recently announced

that it will sell both polystyrene and

copolymers such as SAN, ASA, PA-

ABS blends and ABS terpolymers, as

a single package.

These businesses turned over a

combined €4.5 billion last year,

though it will perhaps not so much

this year. Polystyrene demand is

curently so low that BASF has recent-

ly decided to cut production by 25%

in Q4.

The Ciba acquisition is expected to

make a positive contribution to earn-

ings per share for BASF in the second

year after completion. Hambrecht

refused to detail the synergies he

expects, however.

Since the price agreed is 64%

above the volume-weighted average

share price for Ciba shares in the 30

days prior to announcement of the

offer, one analyst described it as “not

particularly cheap”. Another calculat-

ed that BASF is paying 8.6 times

EBITDA as opposed to typical multi-

ples of 5-6 in the sector at present.

Conversely, this is will below the

11 times EBITDA Dow Chemicals has

agreed to pay for Rohm and Haas in

the other major merger in speciality

chemicals in recent months (SCM,

July-August 2008, page 6).

BASF is universally agreed to have

been the second large chemicals

company to have courted Rohm and

Haas and has also been linked by

rumour to Albemarle in recent

months. This is its first significant

acquisition since 2006, when it spent

€7 billion on Engelhard, Johnson

Polymer and the Construction

Chemicals business of the former

Degussa. Ciba will also be its second

largest ever acquisition after

Engelhard.

News



Ciba succumbs to BASF’s offer

Hambrecht (left) - BASF must play a role in chemicals consolidation; Meyer (right) - Sandwich position getting worse all the time

News.qxp 7/10/08 12:12

News



EUROPEAN UNION

CEFIC, the European Chemical

Industry Association, has recently

been at loggerheads over the REACH

Authorisation process with ChemSec,

an umbrella group of environmental

NGOs. ChemSec’s publication of a

list of chemicals it believes should be

phased out succeeded in generating

media coverage, but CEFIC has called

its intervention unhelpful at best.

On 17 September, ChemSec pre-

sented the so-called ‘SIN (Substitute

It Now) List 1.0’ at a special

‘Substitution Conference’ in

Brussels. This lists the substances it

believes should be given the highest

priority in the REACH Authorisation

process and ultimately substituted by

safer alternatives.

As part of REACH, the European

Chemicals Agency (EChA) had pub-

lished its first, 16-strong list of ‘pro-

posed substances for the Candidate

List’ on 30 June (http://echa.europe.eu/consultations/authorisations/svhc/svhc_cons_en.asp). Consultation

is now taking place up until 22

October, after which these substances

may be included in Annex XIV of the

REACH legislation, making them sub-

ject to Authorisation,

The Authorisation process requires

producers or importers of Substances

of Very High Concern (SVHCs) to

obtain special permission before

placing them on the market. Where

these are used in consumer products

at >0.1% wt/wt, suppliers must dis-

close this and give ‘safe use’ informa-

tion. The EchA has indicated that it

may add substances to the list annu-

ally as testing and data analysis pro-

gresses, though this is far from clear.

ChemSec, the ‘International

Chemical Secretariat’, is guided by

an NGO advisory committee includ-

ing the European Environmental

Bureau, the World Wildlife Fund,

Greenpeace, Friends of the Earth

and others. Its stated aim is to

ensure “that Authorisation is an

effective tool to fast-track the most

urgent SVHCs for substitution and

to facilitate toxic use reduction by

businesses”.

The organisation says that it was

actively involved in the REACH leg-

islative process, working with “pro-

gressive companies”, mostly down-

stream users and retailers, to counter

the voice of the chemicals industry.

Representatives from Dell, Sony-

Ericsson, Sara Lee, Skanska and

Hennes & Mauritz spoke at the

Substitution Conference. They pub-

licly welcomed the ‘SIN List’ and

some have pledged to use it for guid-

ance in their purchasing of chemicals.

(Also launched at this event was a

report entitled ‘Substitution 1.0 - The

Art of Delivering Toxic-Free

Products’. This, ChemSec claims,

“provides an introduction into the

process of chemicals managements

and substitution of hazardous sub-

stances, as well as hands-on exam-

ples from some of the companies we

work with”.)

The full ‘SIN List’ is at www.sin-list.org. It runs to 267 substances,

classified by CAS and EC name.

Some are very large volume products

indeed, including styrene, aniline

and benzene, among others. Some,

as CEFIC pointed out, are actually

intermediates and are therefore not

subject to Authorisation under

REACH.

Of the full list, 220 are included

because they have been classified as

carcinogenic, mutagenic and repro-

toxic (CMR) to Category I or II. A

further 17 have been classified as

persistent, bioaccumulative and

toxic (PBT) and/or very persistent

and very bioaccumulative (vPvB)

and/or CMR, while the final 20 are

said to exhibit an ‘equivalent level of

concern’.

The event certainly succeeded in

attracting attention, with several UK

newspapers covering it as if the ulti-

mate banning of the chemicals was a

done deal. Indeed, the next day, the

Wall Street Journal published figures

from Innovest naming 11 chemicals

companies that would have more

than 2% of their sales at risks if the

full list were to be banned. Innovest

estimated that this would affect 30%

of Ciba’s sales, 26% of BASF’s and

Lanxess’s, 24% of Clariant’s and 18%

of Dow Chemical’s.

CEFIC retorted: “The ‘SIN List’ is a

proposal from a specific interest

group and not part of the overall

REACH legal design; it could poten-

tially contribute to confusion

throughout the value chain.” The

organisation therefore urged all par-

ties, including NGOs, to “follow a

unified approach under the guidance

of the EChA”.

“The responsibility for this

process lies exclusively with EcHA

and the EU member states and

CEFIC believes that any list pub-

lished outside this process might be

confusing and not helpful in estab-

lishing REACH as the centrepiece of

the chemicals legislation,” CEFIC

added.

CEFIC has consistently called for a

science-based approach to EACH

process, including Authorisation,

with wide support in industry as a

whole. Guy Thiran, secretary general

of Eurometaux, the European

Association of Metals, commented:

“The publication of alternative lists of

substances does not contribute to a

sound and scientifically based assess-

ment of substances as required by

REACH.

CEFIC is also continuing to

expand its REACH compliance servic-

es. Over the summer, it has been col-

laborating with IBM to develop

SIEFreach, a software tool to facili-

tate the creation of Substance

Information Exchange Fora (SIEFs)

and encouraging its sector groups to

form consortia, most recently the

Oxygenated Solvents Producers

Association.

Some observers believe that the

NGOs had become frustrated that

the initial SVHC list was so short,

since over 1,000 substances have

been identified as CMR, PBT or of

equivalent concern at different times.

Even many in industry expected the

list to be much longer. The ‘SIN List’

is therefore seen as an attempt to

bounce the EChA into tougher

action.

However, Geert Dancet, executive

director of the EChA, who also spoke

in Brussels, commented that it was

not always clear why particular sub-

stances had been included on the

‘SIN List’. ChemSec said the list it

was compiled “through the com-

bined efforts of public interest

groups, scientists and technical

experts ... based on credible, publicly

available substance information from

existing databases, scientific studies

and new research”, but did not elab-

orate further.

With time running out for the pre-

registration of substances under

REACH, the EChA has revealed that

pre-registrations are running far

ahead of expectations. By

September, over 200,000 substances

had been pre-registered by about

7,500 companies via the REACH-IT

system, according to Dancet. This

followed the introduction of bulk

registration in July, allowing compa-

nies to pre-register up to 500 sub-

stances at once.

In September, the EChA was

forced to revise its earlier advice to

companies, saying that they should

only pre-register substances they ulti-

mately intend to register. This came

about because Chemos of Germany

and Azelis REACH Services of the UK

pre-registered the entire EINECS

inventory of 100,000 chemicals.

The EChA has also appealed to the

European Parliament for more subsi-

dies. Dancet admitted that it is con-

cerned about its finances from 2009

onwards, when initial funding runs

out and it has to pay its way via reg-

istration fees. Companies are finding

unexpected ways around paying and

that this may lead to lower income

than expected.

Your SINs will find you out...

Dancet - Reasons for inclusion unclear

News.qxp 7/10/08 12:12

News



GERMANY

The European Fine Chemicals Group

(EFCG) is increasingly satisfied with

the way regulatory authorities in the

EU and the US are dealing with the

issues it has raised over GMP compli-

ance in the manufacturing of APIs and

the flow of counterfeit drugs over the

past four years.

The association believes that it has

also made significant progress on the

issue of pharmaceutical excipients and

with its own voluntary standards for

the manufacture of fine chemicals,

though continued efforts are needed

to flush rogue players out of the indus-

try.

Speaking at CPhI Worldwide 2008

in Frankfurt in early October, Guy

Villax, CEO of Hovione and an EFCG

board member, said that he had seen

“a 180 degree turn in the way Brussels

is looking at GMP compliance”. This,

he added, had taken place even before

the heparin scandal of early 2008,

though this had undoubtedly acceler-

ated the process of change.

“The driver is the increasing realisa-

tion that contaminated drugs aren’t

just something that happens in Africa,”

he said. “Regulators are taking action,

there are more frequent risk-based,

non-random inspections of facilities

abroad, often where concerns have

been flagged up by suspicions of non-

compliance and whistleblowers.”

Now, the EDQM is carrying out 50-

60 foreign inspections per year, driven

in large part by the French and Italian

authorities, and this is expected to

double in 2009. Another major

change is that the EDQM now sends

CEP holders letters requiring them to

name the manufacturer (of their APIs

and the location of the plants). Filing

false details in CEPs is no longer

something that brokers can do with

impunity.

The EFCG is also anticipating a pro-

posed amendment to Directive

2001/83/EC. This may take forward an

earlier concept paper that envisaged

implementing many of the regulatory

improvements that it has been advo-

cating, including a much more strin-

gent inspection regime in regions with

lower standards than Europe, manda-

tory API fingerprinting, the implemen-

tation of GDP as well as GMP, a licens-

ing system and restrictions on parallel

trading. The EC is expected to make an

announcement during October.

An even more significant long-term

move, said Villax, will be the FDA

Globalisation Act, which is now being

considered in the US Congress,

though it will take three years at least

to become law. Recent months have

seen the FDA announce a doubling of

the number of inspections in 2009

and plans to open offices in China,

India and South America.

The Act, Villax noted, will lead to a

15-fold increase in the number of

inspections even on the 2009 level, as

well as greater stringency during them,

annual user fees to fund the process,

the labelling of drug products to show

the country of the origin of APIs and

the extension of inspection to drug

precursor sites, with stiff penalties for

violation.

Citing recent cases where inspec-

tions led to problems being identified

and very rapid action, Villax conclud-

ed: “Compliance is getting tougher

and will get tougher still. The enforce-

ment - and the perception of enforce-

ment - is becoming increasingly effec-

tive, but we must still urge regulators

to continue their efforts to deter the

rogue element in the supply chain”.

This change also brings challenges,

according to Villax, in that so many of

the plants that supply the world mar-

ket are not in strict compliance and

cannot be replaced overnight.

National medicine agencies are

increasingly obsolete in this globalised

market, despite the valuable role they

still play. Moreover, although Big

Pharma firms still set industry stan-

dards, their market share is being

eroded by generics and there is a risk

of “a growing disconnect between

standards and reality”.

At the same meeting, Allan Laing,

CEO of Pentagon and chairman of

EFCG’s Agrochemical Intermediates

Manufacturers in Europe (AIME) sub-

group, updated progress on the volun-

tary guidelines for the manufacture of

ISO-regulated fine chemicals that

AIME is advocating.

The guidelines were formally

launched at Chemspec Europe in June

(SCM, April 2008, pages 20-21,

July/August 2008, page 47). They form

a proposed set of minimum require-

ments for global manufacturers of fine

chemical intermediates and fine chem-

icals that were originally specific to

agrochemicals but are being extended

to all pharma applications.

Since June, AIME has developed a

Business Integrity Evaluation (BIEn)

template with BSI Management

Systems. This, said Laing, should

enable customers to audit suppliers for

their compliance with the guidelines

and thus make a decision on whether

or not the supplier is reliable and

secure within half a day and without

the need for external consultants.

Plans are to finalise both the BIEn

template and the voluntary guidelines

by the end of 2008, test the template

within AIME during Q4 2008 and Q1

2009 and widen it to other EFCG

member companies during 2009. Its

use will then be spread to other

regions, including the US, Japan,

China and India up to 2011, in part-

nership with manufacturers and other

stakeholders in those regions.

Finally, the EFCG announced the

signing of a memorandum of under-

standing with International

Pharmaceutical Excipients Council

(IPEC) Europe that will lead to closer

collaboration on the development of

a GDP/GMP certification programme

for manufacturers and distributors of

excipients. This will be done by a

joint steering committe of the two

associations, guiding two working

groups in the areas of certification

and auditing.

The EFCG had originally raised this

issue at CPhI Worldwide in 2007, said

Tim Bölke of BASF, issuing a position

paper highlighting the risks arising

from the fact that excipients, which

constitute a far higher proportion of

drug volume than APIs, not being sub-

ject to equivalent standards.

The idea was resisted in some quar-

ters at first, but the heparin disaster

changed the environment completely

and most stakeholders in IPEC

Europe, IPEC Americas and the PQD

have come around in favour.

“We have come a long way in the

past 12 months. Now we have support

from regulators, excipient manufactur-

ers and makers of final dosage forms

on the need to act. Through the work

of IPEC Americas, IPEC Europe and

the British PQG, we expect to come

up with a global standard, have a

European implementation scheme

available and get the first auditors

accredited next year,” Bölke said.

Another important development for

the EFCG at CPhI was its first annual

dinner, with Lonza CEO Stefan Borgas

delivering a stellar keynote address on

the challenges facing the fine chemi-

cals industry. Held in Frankfurt during

the show, this brought together about

260 industry players from EFCG mem-

ber companies - two new members

were announced during the dinner -

and their invited guests.

The dinner will become a regular

feature of the show in future years

though it may ultimately be a stand-

alone event. In time, Villax told SCM,

it will be much more than just a din-

ner: the aim is for it to become a

forum for networking. Albeit on a

much smaller scale, it should function

like the DCAT dinner in the US.

CPhI itself and its co-located events

ICSE and P-Mec Europe attracted

about 1,800 exhibitor stands and,

from early projections, 24,000 visi-

tors, according to the organisers, CMP

Information. It will return to Madrid

in the slightly later slot of 13-15

October 2009, thereafter probably

rotating triennially between Paris,

Frankfurt and Madrid. Indications are

that the much-criticised Milan fair-

ground that hosted the event in 2007

has been dropped as a venue.

EFCG sees “huge change” in official outlook

Villax - Compliance getting tougher

CPhI took place in Frankfurt

News.qxp 7/10/08 12:12

News



In BriefKemira goes to GeorgiaKemira has taken a lease on a new

R&D centre at the Georgia

Institute of Technology’s Tech-

nology Enterprise Park in Atlanta,

which will employ 85. The compa-

ny described this as part of its tar-

get of consolidating 17 R&D sites

into five global facilities by sum-

mer 2009. The others are in

Northern Europe, Continental

Europe and Asia, with one more

to follow in Latin America. All

focus on new technologies for the

pulp and paper, water treatment

and oil and mining industries.

RohnerChem to scale EnCatFollowing on from initial screening

and process development work,

RohnerChem will make the EnCat

encapsulated catalysts developed

by Reaxa on a commercial scale at

its Swiss facilities, thus adding

them to its core technology of

transition metal catalysis. The

EnCat range includes palladium,

platinum and osmium catalysts,

with nickel-based ones currently in

beta trials. They are designed

specifically to minimise metal loss

and product contamination often

found with homogenous catalysts.

Solvias takes overSolvias of Switzerland has been

granted an exclusive licence to

develop, manufacture and market

two ligand product lines from

Evonik: CatASium chiral ligands

and associated rhodium complex-

es for asymmetric hydrogenation

and CataCXium coupling ligands

for industrial-scale C-X coupling.

Evonik will continue to make and

sell the related line of CatMETium

catalysts for metathesis reactions.

Magic carpet rideClariant has opened its new

Global Carpet Centre at Louvain-

la-Neuve, Belgium, bringing all of

its colouration and finishing capa-

bilities in the field under one roof

for the first time. Facilities include

an application lab, rotary and jet

printing steamers, a gum applica-

tor, exhaust dyeing machines of all

kinds, foam application, a continu-

ous dryer and fastness testing

equipment. Belgium was chosen

partly because it is the world’s sec-

ond largest carpet producer.

US

The Delaware Court of Chancery has

ruled that the €6.7 billion merger

between Huntsman and Hexion

Specialty Chemicals must go ahead.

This followed months of legal wran-

gling occasioned by the attempts of

Hexion’s owners, Apollo Management,

to abort the deal.

The court denied all declarations

made by Apollo and Hexion in a suit

requesting to be excused from its obli-

gation to consummate the transaction.

It also rejected claims that Huntsman

was not entitled to a €240 million

break-up fee, that it had suffered a

material adverse effect since signing

the merger agreement and that a sol-

vency certificate or opinion could not

be provided for the combined entity.

The court therefore ordered

Hexion to perform the covenants

agreed, including using all “its rea-

sonable best efforts to take all

actions necessary and proper to con-

summate the merger in the most

expeditious manner practicable”.

This original closing date of 1

October will be extended until the

court determines that Hexion has

complied with the order.

The court also found, according to

Huntsman, “that Hexion had

breached a number of obligations and

covenants under the merger agree-

ment, and that such breaches were

knowing and intentional and directed

by Apollo”. Huntsman is continuing a

€2 billion action against Apollo and its

two partners in Texas for fraud and

tortious interference in causing it to

terminate an earlier proposed deal

with Baell, which later marged with

Lyondell.

The EC and the US Federal Trade

Commission have both approved the

merger, demanding only the divesti-

ture of part of Hexion’s speciailty

epoxy resin operations in Germany to

Spolek of the Czech Republic.

The merger, originally agreed in late

2007 but subsequently delayed, began

to unravel in June, when Hexion

attempted to terminate it on the basis

of an opinion from financial adviser

Duff & Phelps, that the capital struc-

ture for the combined company “is no

longer viable because of Huntsman’s

increased net debt and its lower than

expected earnings”.

The matter went back and for

between courts in Texas and Delaware,

with increasingly bitter recriminations

on both sides. Ahead of the court

hearings, Huntsman shareholders vol-

unteered further financing to expedite

the deal, but Hexion stuck to its guns

and claimed that the combined entity

will be insolvent. As SCM went to

press, it appeared that Apollo was

resigned to going ahead with it.

IRELAND/US

SAFC announced at CPhI Worldwide

2008 in Frankfurt that it had begun

operations at a large-scale API reactor

at its site in Arklow, Ireland, and also

announced details of a newly commis-

sioned suite at its St Louis facility that

will produce high potency API (HPAI)

conjugates for cancer treatment. This

all followed on from the announce-

ment of an expansion at the HPAI facil-

ity in Wisconsin earlier in September

(SCM, September 2008, page 10).

The new hastelloy reactor at Arklow

is 6,000 litres in capacity and replaces

an older 2,000 litre reactor in the P1

building adjacent to the powder han-

dling unit. This will increase total

capacity at the site to 96,000 litres,

with reactors ranging from 250 to

8,000 litres. The amount invested was

not disclosed. Arklow is best known for

its virtually unique capabilities in large-

scale SMB chromatography (SCM, June

2008, pages 17-19).

According to Dr Mike Harris, phar-

ma vice president for Europe, the site is

manufacturing at twice the volumes

that it was two years ago and this

investment was necessary simply to

meet growing demand. The new reac-

tor, he added, will in particular enable

the site to meet demand for a highly

corrosive compound for which the cus-

tomer’s needs have are increasing rap-

idly. Some generic compounds have

also been returning to this and other

SAFC sites after years away in Asia,

Harris revealed.

Two further expansion projects are

anticipated at Arklow, both for comple-

tion in 2009. There will be a 15 kg

capacity pilot-scale filter dryer at a cost

of €1.65 million, doubling capacity for

small-scale API manufacture, alongside

a €1.3 million expansion of the cGMP

warehouse.

The new 550 m2 suite at St Louis will

facilitate the conjugation of APIs to

various targeted delivery molecules,

including monocolonal antibodies. It

will also handle early-stage clinical sup-

plies and handle multi-kilo projects,

with the option there of expanding up

to commercial scale.

“This was a technology-driven

investment,” Harris told SCM. “Via

the former Tetrionics, we are strong

in high potency and Sigma has been

active in proteins for 70 years. We

believe this combination of capabili-

ties is unique. The quantitites

involved are tiny but so are those

used in the therapeutic doses when

the products go commercial, so we

will have to expand again in due

course.”

The previous expansion at

Madison, Harris added, was driven

by the growth in the market for can-

cer treatment. Many biotech firms

are also targeting this market with

new entities, some of which are like-

ly to go commercial, so further

expansion makes commercial sense

in SAFC’s view.

SAFC completes Ireland expansion

Court tells Hexion to complete the deal

Arklow is one of SAFC’s large-scale plants

News.qxp 7/10/08 12:12

News



In BriefEPA gives Swan go-aheadThe US EPA has given its first

manufacturing consent order in

the nanomaterials sector to Swan

Chemical of Lyndhurst, New

Jersey, a subsidiary of the UK’s

Thomas Swan, for its Elicarb MW

multi-walled carbon nanotube

product. This follows several

months of collaboration with EPA

experts and the completion of a

Pre-Manufacturing Notice (PMN).

Further work is ongoing, with a

PMN and consent order for single-

walled carbon nanotubes expect-

ed to follow soon.

Recipe for growthSweden’s Recipharm has added

lyophilisation to its contract phar-

maceutical development and man-

ufacturing services with the acqui-

sition of a facility from Inotech

Labor in Switzerland. This can han-

dle batch sizes of up to 250 litres

of drug substance at a time in a

variety of vial sizes, prepare mate-

rials for clinical trials and support

small-scale commercial drug pro-

duction. Recipharm has doubled

in size in the past year.

PTFE start-up Solvay has opened a new PTFE

unit at the Jiangsu High-Tech

Fluorochemical Industrial Park in

Changshu, near Shanghai. Like an

existing facility in Delaware, this

will make the Polymist brand of

PTFE micronised powder for appli-

cations in cosmetics, high gloss

inks, high performance lubricants

and heat-resistant materials across

the rapidly growing Asian market.

The company described the move

as “consistent with Solvay’s geo-

graphical expansion strategy into

fast growing markets”.

Pharmatek opens facilityPharmatek Laboratories has

opened a new 1,670 m2 facility in

San Diego. This features analytical

and formulation development labo-

ratories, plus cGMP manufacturing

suites for highly potent and cyto-

toxic drug products for use in early

phase clinical trials. The facility

holds a State of California Food &

Drug Branch Drug Manufacturers

Licence and is already working on

an unspecified number of highly-

potent development projects.

UK

Aesica, which runs three sites making

APIs and formulated drug products in

the UK, expanded its footprint consid-

erably in September with the establish-

ment of a new subsidiary operation in

the US and a representative office in

China. The company alraead has more

than 45% of its sales in the US and

sources considerable volumes of raw

materials from China, but has hitherto

done this business through agents.

The US office is in Saddle Brook,

New Jersey, in the heart of the US

pharmaceuticals industry. Like many

other offices of European firms, it com-

prises a senior figure with industry

experience - former Minakem execu-

tive Michael Staff - and an assistant.

Staff was appointed in April and this is

the first subsidiary to be established

outside the UK, Aesica CEO Dr Robert

Hardy told SCM at CPhI 2008.

The representative office for China is

near the centre of Shanghai and is

headed by Joe Zou, formerly of Whyte

Chemicals, who has been sourcing

pharmaceutical materials for export to

Europe for ten years. Its role is mainly

one of QA, according to Hardy, and it

will report into the newly established

Aesica Technical Organisation, which

organises the flow of business from

quote to formulation development.

Aesica was established in 2004,

when Hardy, then a BASF executive,

raised the finance to buy out the

firm’s unwanted multi-purpose API

plant in Cramlington, north-east

England. Since then, it has acquired

two ex-Big Pharma facilities in the

UK, one from Merck Sharp & Dohme

in Ponders End, North London, and

another from Abbott Laboratories in

nearby Queenborough that has both

high potency and formulation capa-

bilities.

This has quadrupled turnover from

25 million to a projected €130 million

this year but Hardy still aims to

increase this to €390 million by 2011.

Acquisitions will be the driver for this

and Aesica expects its next major buy

to be in the US, depending on finding

the right facility and reaching a supply

agreement from the former owner to

keep it running until other business is

built up. It looked at many others

before making its latest acquisitions, he

said.

Aesica on three continents

Hardy - Planning to treble in size

ARGENTINA

Umicore’s Precious Metal Chemistry

(PMC) business formally opened its

new platinum API facility in Buenos

Aires, Argentina, on 5 October in the

presence of the Crown Prince of

Belgium and other dignitaries.

The plant is expected to produce

the first batches by the end of 2008.

It makes three platinum-based APIs

for oncology treatment, cisplatin,

carboplatin and oxaliplatin. Umicore

is the world’s largest recycler of pre-

cious metals and cites its closed loop

production and the ability to offer

assured supply at hedged prices as

key strengths in the field.

Umicore’s Christophe Le Ret

explained that the investment was

made with export markets in mind.

The company had been making plat-

inum-based APIs at another site in

the city for ten years and is by far

the leading producer in South

America but this site only supplies

the South American markets. The

aim with the new facility is to man-

ufacture to cGMP and get audited

by the US FDA and the EDQM in

order to offer such services as DMFs

as well as API manufacture to global

customers, he said.

US/CHINA

Arsenal Capital Management, a New

York-based private equity buyer with

a number of mid-sized chemicals

industry interests has agreed to

acquire the Fine Chemicals business

of Ferro for €48.6 million in cash.

The deal is expected to close in Q4,

subject to regulatory approval and

the usual closing conditions.

The business, which turned over

€40.5 million in 2008, employs 140

at sites in Baton Rouge, Louisiana,

and Suzhou, China. It will be

renamed Novolyte Technologies. It

produces electrolytes for the lithium

batteries used in hybrid electric and

electric vehicles, ultra-capacitors and

other energy storage devices, special-

ity solvents and phosphines, while

also offering the contract manufac-

ture of fine chemicals

John Televantos of Arsenal com-

mented that the Novolyte “has a

unique portfolio of strong and high-

ly regarded products and technology

that will be better positioned as a

stand-alone company to take advan-

tage of global opportunities”.

General manager Edward Frindt,

who has also served as Asia business

director of Ferro and oversaw the

start-up of its battery materials plant,

has been named CEO.

Arsenal is the owner of Velsicol

Chemical, a major global manufac-

turer of benzoic acid and derivatives

for agrochemical, food and beverage

uses and non-phthalate plasticisers

and is seeking to acquire DSM

Special Products, a maker of special-

ity food, feed and pharmaceutical

ingredients, though competition

issues have been raised. Earlier, it

created Vertellus Specialties by merg-

ing Reilly Industries with Rutherford

Chemicals, selling it on to Wind

Point Partners last year.

For Ferro, CEO James F. Kirsch

said that, as well as debt reduction,

the company is making the sale to

focus on core capabilities of particle

engineering, formulation and colour

and glass science. “Fine Chemicals

consists of a number of smaller busi-

nesses that do not effectively lever-

age the scale of Ferro’s core per-

formance materials operations,” he

commented.

Set in platinumFerro Fine Chemicalsadded to the Arsenal

News.qxp 7/10/08 12:12

News



In BriefBrenntag takes overRhodia has signed a “partnership

agreement” with Brenntag, one of

the world’s largest chemicals distrib-

utors. Under this, its distribution

network in South-East Asia, India,

Australia and Taiwan, including the

180 people employed in it, has

been transferred to Brenntag. Only

Rhodia Novecare products in the

Indian market have been retained.

The company said that this “brings

new perspectives for efficiency”.

A sound partnershipProsonix of the UK has announced

a new deal under which Syrris will

be the main marketing channel for

its new SonoLab laboratory-scale

sonocrystallisation and sonprocess-

ing equipment. This is based on the

same bonded transducer-based

design as its commercial-scale

Prosonitron equipment, which

Pfizer recently agreed to implement

in controlled crystallisation in pri-

mary API manufacturing at its sites

in Ireland, following on from trials

at Pfizer Global R&D in the UK.

China takes its vitaminsVertellus Specialties has announced

plans to expand vitamin B3 pro-

duction in China in response to

growing demand from the human

and animal nutrition markets

across Asia. It will break ground on

a 7,000 tonnes/year 3-cyanopyri-

dine plant at Nantong in early 2009

for completion by the end of the

year. A niacinamide and niacin

facility will follow later. Vertellus

has already booseted capacity for

β-picoline raw materials for vita-

mins in the US and China.

CLEAR future for batteriesFMC Lithium has opened its Centre

for Lithium Energy Advanced

Research, of CLEAR. This is an

R&D facility at its site in Bessemer

City, North Carolina, which

includes a dry room for the testing

of rechargeable lithium-ion battery

components. It will be used to

develop and demonstrate FMC’s

lithium battery materials, notably

its new SLMP brand of stabilised

lithium metal powder. The compa-

ny has been active in lithium ion

battery tecnology for nearly 20

years and sees strong growth

potential for it in the coming years.

UK

Close Brothers Private Equity

(CBPE), a UK-based investor which

specialises in chemicals companies

worth up to about €200 million/year,

has made significant changes to its

portfolio.

During September, it provided just

over half of the finance for a man-

agement buy-out at Warwick

International, while also selling its

BWA Water Additives operation to

United International Bank (UIB) of

Bahrain. Both firms are UK-based.

CBPE provided just over half of

the finance for the buy-out of

Warwick International from Sequa of

the US. The rest is coming from a

group of four UK banks headed by

the Royal Bank of Scotland that is

backing CEO Bob Ellis and his man-

agement team. CBPE will have two

board members at Warwick, one of

them non-executive.

Warwick turns over €227 mil-

lion/year and has seen strong growth

in the past ten years as its key prod-

uct, tetra acetyl ethylene diamine

(TAED), has become increasingly

accepted by detergent major produc-

ers across Europe and the Far East.

TAED is also used in peroxygen

bleach activators. The company

recently added the Malaysian distrib-

utor GME to its distribution arm,

which stretches from Europe to

Brazil, China and South Africa.

BWA, which CBPE previously

bought from Chemtura has been

acquired by UIB, a Shari’a compliant

investment bank, with funding from

the Royal Bank of Scotland and

HSBC. Terms were not disclosed.

The company produces speciality

chemicals for water treatment,

notably to control and prevent corro-

sion of iron or steel and inorganic

deposits on the surface of pumps and

pipes and to treat microbiological

growth in process water. These prod-

ucts are mainly used in water desali-

nation, industrial water treatment

processes and secondary oil recovery.

BWA is active in over 85 coun-

tries. Its strong presence in the

Middle East market was a key moti-

vator for the acquisition according

to UIB, which added that it will

“support BWA in its drive through

the next phase of growth”. The com-

pany had recently invested signifi-

cantly in both infrastructure and

personnel.

“Taking into consideration the

Middle East region and in particular

the GCC economic growth and the

dynamics in the water treatment

market, it was imperative that we

explored fresh funding to support

our expansion plans and grow fur-

ther,” added Dr David Cartmell, CEO

of BWA.

Previously CPPE had bought and

sold several other firms in this field.

Chance & Hunt was acquired from

ICI and sold to Azelis, while Aroma

& Fine Chemicals (A&FC) was

acquired from International Flavours

& Fragrances and later sold to

Innospec Specialty Chemicals.

Close invests in Warwick, sells BWA

CHINA/INDIA

Dishman used CPhI Worldwide 2008

to announce details of a new €7.03

million production unit in Shanghai

that it expects to open in Q2 2009. Its

CarboGen-Amcis subsidiary is also

continuing work on the large-scale

high potency facility at the main site in

Bavla, near Ahmedabad in India.

The new Chinese facility covers

80,000 m2 of the Shanghai Chemical

Industrial Park and is arranged in four

segregated suites that can be inter-

linked, each with a Class 10,000 prod-

uct separation and drying area. Key

features will include ten reactors of

2,500-8,000 litres capacity in all of the

standard materials and covering the

temperature range from -20 to

+160˚C, plus centrifuges, an agitated

pressure Nutsch filter dryer, fluid bed

dryers and a rotary vacuum dryer.

As well as manufacturing, this will

be Dishman’s main administrative cen-

tre in China and will have QC capabili-

ties for raw materials, intermediates

and APIs. The warehouse will have

fully segregrated areas for raw materi-

als and finished products, plus dedicat-

ed sampling suites, quarantine areas

and both cool and refrigerated storage.

“We wanted to have a second supply

source for customer security,” said Jose

Benito, marketing manager for

Dishman Europe. Recent security

problems in Ahmedabad and the noto-

rious ‘Olympic effect’ in China might

make some customers wary of relying

on a producer present in only one of

the two. Demand was the other key

driver. “It will take some time to fill the

site to capacity but we are confident we

can do it,” she added.

Dishman continues to invest heavily

in its home market too, with

CarboGen-Amcis due to bring the new

€9.5 million high potency facility at

Bavla onstream early in 2009 The

4,300 m2 facility will make both cyto-

toxic and non-cytoxic HPAIs.

It has been designed to the same

principles as the existing high potency

facility in Bubendorf, Switzerland. Four

separate cells are all being fitted with

three reactors and a filter dryer, oper-

ating to Category 3 and 4. Reactor

sizes will range from 630 to 1,600

litres. There are also contained labora-

tories and space for further manufac-

turing cells.

This is the single largest among

€18.4 million of investment by

CarboGen-Amcis in the fiscal year to

April 2009. It has also expanded low

temperature reaction capacity, upgrad-

ed the Category 3 containment area

and installed a 30 cm chromatography

column at Bubendorf. At Manchester,

UK, it has added a new kilo lab with

two 30 litre glass vessels and a new 46

cm chromatography column.

Unlike most of the European opera-

tions acquired by Indian firms,

CarboGen-Amcis has retained its exist-

ing identity. Its own sales team will

take charge of marketing the services

of the new facility to its existing cus-

tomer base. However, the offer is

increasingly integrated, with

CarboGen-Amcis offering develop-

ment and scale-up then passing proj-

ects on to Dishman for large-scale

manufacture. This has already hap-

pened in a number of projects, accord-

ing to Benito.

“We had requests from customers

for projects that were too big for the

Swiss facility to handle,” added Rhona

McIntyre, commercial director at

CarboGen-Amcis. “There is more big

volume work in high potency than we

originally realised and some of the

APIs are made in quite large volumes.

This facility will be enough to meet

demand for the near future.”

Dishman builds first China unit

News.qxp 7/10/08 12:12


Agrochemical intermediates


A quiet giantWeylChem has emerged as a major player in agrochemical custom manufacturing. AndrewWarmington spoke with managing director Georg Weichselbaumer

WeylChem, a supplier of custom manufac-turing services to the agrochemicals, spe-ciality and non-GMP pharmaceuticals

sectors, is surprisingly little known in the chemicalsindustry. That reflects in large part the low-keyapproach of its owner, the International ChemicalInvestors Group (ICIG).

However, this obscurity cannot last, given ICIG’sstated ambition to turn over €1 billion/year and thatWeylChem has itself grown its sales by 70% in eachof the past two years. As well as being a top 20 firmin fine chemicals, WeylChem is a top five player inagrochemical custom manufacturing and has beenriding the wave of recovery that this seemingly mori-bund market has enjoyed of late.

Frankfurt-based ICIG itself is headed by PatrickSchnitzer and fine chemicals industry veteran, DrAchim Reimann, who formerly ran the consultingoffice of Arthur D. Little in Europe. It only emergedthree years ago but is already a serious player in thefine and speciality chemicals industry, operating 15separate subsidiary companies with 19 manufactur-ing plants, 11 of which are in Germany.

These were acquired from seven different previ-ous owners, employ some 3,000 people and turnover about €600 million/year. ICIG says that it con-centrates on “mid-sized chemicals businesses, prefer-ably subsidiaries of large corporations operating incompetitive environments, which were considerednon-core and acquired at low multiples”. Such con-siderations have informed all of its acquisitions, ofwhich WeylChem was among the first.

The name WeylChem derives from Dr Carl Weyl,who founded a tar distillation firm in Mannheim,Germany, in 1877. This firm had long since beensubsumed into Rütgers Chemicals but the name wasreadopted for the two operating companies ofRütgers’ Fine Chemicals division in Germany and theUS when ICIG bought them in June 2005.

Simultaneously, ICIG acquired three other divi-sions from Rütgers: the wood preservatives and fireprotection arm, which continues as RütgersOrganics; Rütgers CarboTech, now known asCarboTech AC, which makes activated carbon andmolecular sieves for the water and gas industries;and the US-based Performance Chemicals division,which is now called Nease. Collectively, the five divi-sions had turned over €85 million in 2004.

Later in 2005, ICIG acquired Wuppertal-basedEnka from Acordis. Enka is the world’s largest makerof viscose filament yarn for textiles turning over€100 million/year from four sites in Germany andPoland. After a brief lull in 1H 2006, other acquisi-tions followed, turning ICIG decisively in the direc-tion of fine chemicals.

At the end of August 2006, it agreed to buy the200-year-old site in Thann, eastern France, fromAlbemarle. This is now known as Potasses et

Produits Chimiques (PPC) andits fine chemicals activities arefully integrated intoWeylChem.

Next, in October 2006, ICIGacquired Cambrex Cork inIreland and CambrexProfarmaco Landen in Belgiumfrom Cambrex’s Human Healthdivision. Now known as CordenPharmaChem, these make smallmolecule APIs to GMP stan-dards and have combined salesof about €34 million/year. Inthe year following the acquisi-tion, according to WeylChem,they increased their sales by20% thanks in part to the introduction of a product-specific sales force.

In May 2007, there followed the acquisition ofClariant’s German- and US-based CustomManufacturing Business. This business had sales of€135 million in 2006 and employed 490 people,producing intermediates and active ingredients forthe agrochemicals, pharmaceuticals and polymersindustries; Clariant’s GMP custom manufacturingactivities for pharmaceuticals continue under differ-ent private equity ownership as Archimica.

With this business arrived Dr GeorgWeichselbaumer, who had been business director ofClariant Custom Manufacturing. He was soon afterpromoted to be joint managing director ofWeylChem, alongside former Rütgers executiveThomas Büttner.

At WeylChem, Weichselbaumer now takes chargeof all product and key account management andnew business development and is generally the pub-lic face of the company. Büttner is more internallyfocused. Other board members head up operations,R&D and administration.

Adding Clariant Custom Manufacturing was thereal transforming deal for both WeylChem and thewhole of ICIG, according to Weichselbaumer. Itbrought in a lot of advantages, such as “a strong andexperienced management team, well trained inHöchst and then Clariant, well-maintained assets instrategic locations, a broad technology base and aglobal marketing presence.”

WeylChem is now a six-site operation with 2,430m3 of non-GMP reactor capacity in Germany, theUS and France. The former Clariant businessaccounts for about 75% of its revenue and capabil-ities; the former Clariant sites at Höchst andGriesheim in the Frankfurt region, which both dateback over 150 years, have capacities of 950 and200 m3 respectively in glass-lined and stainlesssteel reactors of 6-16 m3. They employ a total of270 people.

Griesheim, which is by far the larg-er of the two sites, has a 20 bar reac-tor and special waste water treatmentcapabilities, as well as being the site ofa pilot plant and a ‘mini-plant’ operat-ing at up to 200°C. The R&D labora-tory here produces at scales up to 5litres, operating at up to 220°C and200 bar.

Core technologies in Germanybegin with side chain and ring chlori-nation, the former being carried out at7,500 tonnes/year scale in four chlori-nation lines and two hydrolysis lines atHöchst. Others include catalytic oxida-tion, patented halex reactions for theproduction of fluoroaromatics, distilla-

tion at up to 200°C with 100 theoretical plates in adedicated separation plant for both batch and contin-uous reactions plus associated melt crystallisationunits, Ullmann, Sandmeyer and Friedel-Crafts reac-tions and downstream diazotisation chemistry. Thereis also a long list of support reactions.

At Mannheim, the former Rütgers Chemicalsoperations that grew out of the original FabrikLindenhof C. Weyl now employ 140 people andhave 130 m3 of capacity in glass-lined and stainlesssteel reactors of 0.8-8 m3, plus distillation units withup to ten theoretical plates. Special equipment hereincludes a tube reactor. There is also an R&D lab anda kilo lab operating at up to 250 litres.

Key reactions are Mannheim include chiral enzy-matic reductions, cyanations, oxidation, chlorination,nitration, Bouveault-Blanc reactions and palladium-catalysed carbonylation, as well as many supportreactions. The plant also had a long history in multi-step custom manufacturing and carries out hazardassessment.

Weichselbaumer - Cashflow is high

Distillation towers at Griesheim

Weylchem.qxp 7/10/08 12:13




WeylChem also has former Clariant and Rütgersoperations in the US. As in Europe, the former is byfar the more important. The ex-Clariant multi-pur-pose manufacturing site at Elgin, South Carolina,employs 210 people and has 850 m3 of reactor vol-ume in glass-lined and stainless steel reactors of 8-16m3 with18 distillation plates.

Notable features here include five solids handlingunits, a Hastelloy centrifuge and dryer and a 2,500litre pilot plant that operates between -50°C and+230°C and at up to 6 bar. There is also a 50 litreR&D lab. The former Rütgers site in Augusta,Georgia, by contrast, employs 45 people and has120 m3 of capacity. The key feature here is a hot oilhigh-pressure reactor

Core competencies at the two US sites includeSkraup quinolines, high-pressure hydrolysis, bromina-tion, Suzuki and Grignard coupling, carbonylation, theUllmann reaction and Diels-Alder cyclisation. Theseare supplemented by various others, including halo-genations, Friedel-Crafts reactions, chloromethylation,allyl esters, nitration and epichlorohydrin chemistry.

Elgin is also the site at which WeylChem willimplement its recently announced plans to producea complete series of Grignard reagents on an indus-trial scale as demand grows and customers areincreasingly unwilling to make these reagents them-selves. The site has dedicated 15,000 and 10,600litre production lines for Grignards. This is the first ofthe product businesses that WeylChem will establishin order to be less vulnerable to the ups and downsof the custom manufacturing industry.

The company’s commercial-scale Grignard rangecovers EtMgBr, EtMgCI, 4-toyl MgCI, phenyl MgCI,neophyl MgCI, t-butyl MgCI and isopropyl MgCI (allin THF) plus MeMgBr, cyclohexyl MgCI and N-butylMgCI (in THF/toluene). These are used in the for-mation of C-C, C-P, C-Sn, C-Si, C-B and other C-het-eroatom bonds in the manufacture of pharmaceuti-cals, agrochemicals and other complex products.

WeylChem’s final site, PPC in Thann, has a relative-ly small fine chemicals business. Total capacity is 180m3 in glass-lined reactors of 8-16 m3 and it is mainlyfocused on bromination to produce brominatedaliphatics, aromatics, acid and esters and brominationreagents.

Other capabilities at Thann, which employs 350people in total, include chlorination to produce awide range of chlorination agents, plus hydrobromi-nation, the Wittig reaction, air-sensitive synthesis andelectrolysis. There is a 1,000 litre pilot plant and a 12litre kilo lab. One notable feature is a Halar-coatedcentrifuge.

WeylChem has now realised the synergies avail-able between its operations and has integrated themfully, Weichselbaumer says. Specifically, he mentionstwo big projects where the capabilities of differentsites have already been used in a way that would nothave been possible before. One was in polymers, theother in biofuels.

Naturally, different company cultures have been achallenge already the way, but Weichselbaumerbelieves that the more significant cultural differencesare those between operations in Germany, Franceand the US. “You cannot and should not try tochange these,” he says.

The biggest differences he has seen in his owntransition from Clariant to WeylChem have beenthose arising from the move from a big chemicalscompany with a lot of financial muscle and a long-term plan to one owned by an institutional investor.There is less of a ‘big company attitude’; layers ofbureaucracy have been removed.

“At WeylChem, we do and spend what is neces-sary and no more,” says Weichselbaumer. A lowerstandard is acceptable, he adds, if it is less costly andmeets what is necessary - obviously there must be nocompromise on safety and production.

Financially, matters are also very different. Controlof cashflow is now the key measurement and theresponsibility of every manager of a site. Investmentdecisions have been delegated down the line.“Everyone can see what the costs are and managingthem is a big responsibility for all of the managers,”Weichselbaumer adds.

At Clariant, by contrast, EBIT was the key meas-urement and the delegation of investment decisionstook place at a much higher level. EBIT is importantat WeylChem too - there is a stated target for EBIT-DA margin of more than 10%, but there is nowherenear the same emphasis on it and how this isachieved is left up to the management.

In large part, this is down to Riemann’s style ofmanagement. Weichselbaumer remembers that,within a month of the acquisition going through, hewent to Riemann to ask for a fairly substantial invest-ment project with an attractive payback time.

“Dr Riemann said to me ‘What are you doing hereasking? Just go and do it’. So a decision that mighthave taken three or four months at Clariant wasmade in a day”, he says.

Although Riemann and other ICIG officials playno part in the day-to-day running of the subsidiaryoperations, he knows the industry and its key playersextremely well. Weichselbaumer notes: “He can con-nect things from different sites to achieve outcomesthat would not have been possible with one plant.”

WeylChem does not have a central R&D function,nor does it carry out basic R&D. All the work it doesis on the development and optimisation of customer-specific processes and is carried out site-by-site, withone person working across the whole company toensure that different research projects are carried outat the site best suited to them.

The company does not break down its finances inany detail, but it is known that ICIG’s businessesturned over some €600 million last year. The finechemicals operations - which are not limited toWeylChem, of course - accounted for about half ofthis and agrochemicals were more than half of theWeylChem total, which suggests a business in thisfield north of €100 million.

Weichselbaumer believes that WeylChem is in thetop five suppliers of intermediates, active ingredientsand custom manufacturing services to the agro-chemicals sector. Saltigo is the clear leader in thismarket, with KemFine, DSM and Lonza the others.Unlike some of these, WeylChem is currentlyfocused mainly on customer-specific projects, thoughthis is beginning to change with the establishment ofthe first product line.

For a decade and more, the agrochemicals indus-try seemed to be in a tailspin of declining sales thatbottomed out in a dreadful Q1 last year, when virtu-ally no enquiries were coming in. The subsequentrecovery took many by surprise and the reaction forthe first three to six months was cautious, if notdownright cynical.

“One year ago, there was a strong belief that therewas ‘enough steel in the ground’. The focus was onfiling empty vessels,” says Weichselbaumer. Now hebelieves, looking at the sustainability of the underly-ing factors in the market, that the industry could con-tinue to do well for the next three to five years.

‘Well’ in this context means growth of 2-5%/yearand more than this for the custom manufacturingsector. This figure hardly seems unrealistic, given thatfuture demand for some of the intermediatesWeylChem supplies almost doubled within the spaceof a few months in 1H 2008.

This was fuelled by a mixture of factors: the needto grow ever more food to feed the world; the neardoubling in prices for agricultural commodities andthe consequent maximisation of yields by theincreased use of agrochemicals and expansion offarm areas in Europe and South America in particu-lar; the opening up of the markets in China, Russiaand Eastern Europe; and, increasing demand formeat in China.

Biofuels have been another factor because theycompete for land with the food industry, thoughWeichselbaumer cautions against assuming that theywill carry on growing indefinitely. “This is an unreli-able factor driven by politics and is subject to changeas governments change,” he says.

Moreover, the most modern agrochemical prod-ucts, Weichselbaumer points out, are in highdemand. This is because many older ones - abouthalf of the current total of 500 by most estimates -are not being re-registered under the PlantProtection Products Directive because of the exces-sive cost of doing so. They will therefore need to bereplaced somehow.

Manifolds for the separation of distillation cutsfrom the halex reaction





This process could fundamentally change the tra-ditional paradigm that very few new agrochemicalsreach the market, because every conceivable functionfor them was already supplied at least adequately. Thepossibility is now there of unmet needs that have tobe addressed. Many of the new products in the high-est demand have synergistic effects, such as strobil-urin fungcides that also increase plant yield.

Another important factor in the growth is the roleof China. “One year ago, China was only a threat,now it is an opportunity as well,” Weichselbaumersays. This, he believes, reflects both increasingdemand in China itself and the decreased competi-tiveness and reliability of the Chinese supply chain.

Chinese producers no longer have such a costadvantage over Westerners, thanks to the reduc-tions in export subsidies, the strong Yuan andincreasing costs. Most recently, the ‘Olympic effect’led to many chemicals being suddenly unavailableon more or less arbitrary grounds and highlightedthe vulnerability of Chinese supply lines to thewhims of the state.

WeylChem has seen instances of customers trans-ferring production to Chinese suppliers only to seethese close down. Some Chinese firms have fallenvictim to the government’s increasing pressure tomove into chemical parks where it provides the infra-structure, others to the increasingly stringent enforce-ment of environmental legislation and crackdownson corruption.

Of course, China will remain a major supplier ofagrochemical raw materials and active ingredientsbecause the government wishes to encourage thegood producers and drive out the bad ones - andthere are plenty of good firms there. India is anotherincreasingly important player.

“Our customers are turning more to India andIndia could be an even bigger factor, if it could getits infrastructure problems under control,”Weichselbaumer says. “We are working with quite afew suppliers in India. In fact one of our biggestrecent projects was the relocation of a small air oxi-dation unit to India, which makes the technologyavailable again for our customers.”

Not everything is positive, of course. Like every-one else, WeylChem is coping with huge increases inthe costs of energy and raw materials, notably themany it uses based on potassium, sulphur and phos-phorus.

To cope with this, it has had to increase prices by20% or more in some cases, including contractedproducts. Customers are amenable to this, though,because they are currently focused more on avail-ability than price.

All in all, then, business is good for WeylChem atthe moment. “We have a huge second half ahead ofus,” says Weichselbaumer. Indeed, the company isnow running hard to meet the increase in demand,in part because of the initial wariness to believe thatthe sudden upsurge would last.

“We had to change how we ran the business andit also needed a change in mindset - many in themanagement team had only known decline. For sixmonths or so, we hesitated, but now we are gainingin confidence as we see the recovery happening andare getting customer feedback,” he adds.

To this end, the company has been working todebottleneck equipment, in order to have dedicatedlines and higher capacities and therefore producemore efficiently, or adding new equipment withinexisting buildings. These investments are generallydedicated to specific products, some of which are itsown. They are “largely self-funded and internallydecided”, says Weichselbaumer.

Quite a few projects have been planned, he con-tinues, that require customers to guarantee take-upor part-finance the investments to the tune of sever-al million Euros. And they are generally willing to dothis - some will even pre-fund investments becausethey believe that they will pay for themselves withina year. Many, chastened by finding that carrying lowlevels of inventory had left them vulnerable, areagain prepared to pay for security of supply.

This situation may ultimately lead to WeylChemacquiring more capacity, Weichselbaumer adds. “Theapproach is cautiously optimistic. We need to bal-ance the rush into building new assets with the defi-nitely increased demand from our agrochemicalscustomers. As the positive outlook for the sector isshowing strength, the focus is on acquiring assets inthe market place with low utilisation and a matchingfootprint.”

However, he also cautions that, although this isnow a suppliers’ market rather than a customers’market, the difference is not so vast. “We are in thistogether and we both need to make things happen,rely on each other and act to ensure we don’t doanything stupid. This isn’t a business that changesfrom day to day.”

With the pot of gold at the end of the pharmarainbow looking more elusive than ever, might notthe fine chemicals industry pile back into the revivedagro market? After all, the non-GMP custom manu-facturing services WeylChem and its competitorsoffer are not rocket science by comparison withGMP pharma manufacturing.

Weichselbaumer doubts it. “There is a small sup-plier base but I don’t see many others coming

back,” he says. “There are big entry barriers in agroand you need vessels of a certain size. People arestill very wary of installing new equipment,” hesays.

ICIG has continued to rearrange its portfolio sincedigesting Weichselbaumer’s former employer,though the scale has been much smaller and noneof the changes have been in the agro field.

In April 2007, it made its first divestment, sellingthe Pyrion fungicides and bactericides business unitto Janssen Preservation & Material Protection, a divi-sion of Belgium’s Janessen Pharmaceutica, togetherwith a toll manufacturing agreement.

Miltitz Aromachemicals, the former Leipzig-MiltitzDuft & Aromaproduktion, a small maker of synthet-ic aroma chemicals that also offers custom hydro-genation and distillation services to the flavours andfragrances, was the next acquisition in July 2007. Thisis currently ICIG’s only presence in flavours and fra-grances.

Milititz was followed by the acquisition of Synkemfrom Solvay subsidiary Laboratoires Fournier inNovember 2007. Synkem makes APIs and offerscustom manufacturing from a site in Chenôve,France, with 45 m3 of capacity plus a 10-130 litre kilolab and a 100-2,500 litre pilot plant. Its name has notbeen changed.

The final acquisition to date, also in November2007, was AstraZeneca’s site in Plankstadt, Germany.Now called Corden Pharma, this facility makes soliddosage forms with special expertise in the purifica-tion of APIs and the formulation of potent products.

This acquisition, ICIG said, means that its sub-sidiaries cover the whole pharmaceutical value chainfrom basic chemicals, fine chemicals and non-GMPintermediates (via PPC and WeylChem) to APIs andfinal dosage forms (via Corden PharmaChem,Synkem and Corden Pharma).

2008 has been a year for ICIG to digest its newacquisitions but Riemann has remained bullish aboutfuture acquisitions. At Informex 2008 in NewOrleans, he said that the company is seeking evenlarger-scale buys in order to continue its two-figuregrowth rates and has the cash available to make thispossible. Both GMP and non-GMP assets are underconsideration, he said.

The key targets are to push sales above €1 bil-lion/year and ICIG will mainly look for firms that cangive it access to new technologies and/or synergieswith its existing firms. ‘Missing’ technologies likephosgenation and gas phase fluorination are strongpossibles. The current situation had made buys inChina less appetising, according to Riemann.However, this story clearly still has some chapters leftto write.

For more information, please contact:Dr Georg WeichselbaumerWeylChem Frankfurt GmbHStroofstrasse 27D-65933 Frankfurt-am-MainGermanyTel: +49 69 38 00 25 00E-mail: [email protected]: ww.weylchem.com

Large reactor for agrochemical active ingredients


Project1 7/10/08 12:26 Page 1

Despite a mostly hostile media,a more demanding regulatoryenvironment, defensive man-

ufacturers and a dearth of good newproducts, the sometimes malignednon-crop user of pesticides has con-founded the aspiration of governmentsand continues to purchase and applymore of these products.

Perhaps this is because they find theproducts effective in getting rid of bugs,rats and other pests, so improving thequality of life at home and in the work-place! Legislation may deter them but,unless the products are banned out-right, ordinary citizens will continue touse them, not least because there areno adequate alternatives to deal withmany pest problems.

It is not as though demand has beenboosted by aggressive or extensiveadvertising. Outside North America,there is virtually no promotion of non-crop pesticides in the general media,print, radio or TV. Nor have manymanufacturers invested heavily tobring out attractive new lines; mostnon-crop products are barely distin-guishable from their agricultural pre-cursors.

No, users wants fewer nuisancepests around, especially if they may becarriers of disease - as will be discussedlater - and they have been prepared to

go out and purchase products withwhich to do something about it. All thishas produced quite some growth overthe past few years.

20 years of expansionIn the early 1990s the non-crop pesti-cides industry was worth, at best,US$8-9 billion at end-user level. No-one knew for sure - little marketresearch was done - and it was certain-ly not a strategic element in the devel-opment of pesticides.

Now, according to the sixth cycle ofglobal studies carried out byAgricultural Information Services (AIS)in its Global Non-Crop MarketProgramme, the market was valued at$21 billion in 2007. Growth had beenaround 4-5% per year until 2003,since when it has doubled in local cur-rency (and more in US dollars).

In volume terms, growth has beeneven greater, since prices of non-croppesticides have fallen on average byaround 20% since 2003. The mostrapid expansion has been in develop-ing countries such as China, India andColombia. Surprisingly, though,France, Japan, the US and other moremature markets have also grownstrongly.

The home insecticides market is eas-ily the largest segment, but virtually all

the other 45 segments have alsoexpanded strongly from timber pre-treatment to golf courses, and fromPCOs to mosquito control.

Even so, global average expenditureremains low at $2.95/head/year, withthe USA near the top at $20, Franceand the UK at $10, down to China at$1.20 and India $0.50. This suggestsscope for further growth, given that thefigures for China and India in 2003were $0.50 and $0.15 respectively.

What does non-crop include?Before looking at what is behind thisgrowth, a few facts will illustrate non-crop’s make-up. The home and gardenmarket is by far the most valuable part,accounting for most of the Self-Applied segment. Its share has evenincreased slightly since 2003 (Figure 1).

The Industrial segment includesweed control on railways and road-sides, in and beside waterways and inother places where it is necessary toremove all vegetation. Much of this isunder the control of governments,which are looking in general for waysof reducing pesticide use. They aretherefore broadly against herbicides,but the alternative of mowing is prov-ing contentious for both economic andenvironmental reasons.

Forestry and Timber Treatmentexperienced growth of 5% and10%/year respectively between 2003and 2007. Increased demand for tim-ber in construction and the appeal oftimber as a renewable resource havedriven this rise, which looks likely topersist once the current dip in con-struction is behind us.

The Pest Control Operator (PCO)segment also grew by a healthy10%/year over the same period. PCOsoffer a professional solution to peoplewho want to keep their homes pest-free but do not want to apply pesticidesthemselves. They can also work toagreed norms across frontiers, makingthem attractive to multinationals likehotels who want their brand to operateto the same standards of hygieneworldwide.

The nursery and ornamentals busi-ness forms the largest part of theSeasonals market. Demand for cutflowers, bulbs, potted plants, trees,shrubs and other plants grown com-mercially for sale as gifts or for amateurgardeners to plant out has expandedfast. With it, the use of pesticides hasincreased at 16%/year since 2003, wellabove most other segments. This alsosays something about the growth ofgardening as a leisure pursuit.

Public Health is in some ways themost difficult part of the market toanalyse, because the incidence ofmalaria and comparable diseases isunpredictable and the speed ofresponse and the scale of resourcesdeployed is intensely political andhence volatile. Nonetheless, there hasbeen growth in this market as govern-ments have spent more overall than inthe past. A major recent development(see below) will alter this market forev-er and boost the use of insecticidessubstantially.

The chemistryInsecticides represent 55% of all non-crop products - a proportion that hasnot changed for some years.Herbicides come next with 28% andare especially important for industrialvegetation control on railways and thelike. Fungicides and bactericidesamount to 10%. The rest includesrodenticides, molluscicides, plantgrowth regulators and repellents.

Over 750 active ingredients areapplied in more than 7,000 registeredbrands, with a concentration around afew key insecticides and herbicides,such as permethrin, allethrin andglyphosate. Mosquitoes, ants, termites,flies and cockroaches account for over30% of non-crop pesticide use, rodentsfor 4% and total vegetation controlanother 10%. Over 1,000 other insects,weeds and diseases make up theremainder.

Around 90 different formulationtypes are found in branded non-cropproducts. As the commonest presenta-tion for household insecticides, aerosol




Non-crop pesticides on themoveRod Parker of market research and consultancy firm Agricultural Information Services highlightsremarkable developments in the non-crop business for pesticides and argues that we are likely tosee more of this

Self-applied 63% (13,305)

Turf 8% (1,694)

PCO 7% (1,572)

Seasonal 6% (1,234)

Timber treatment 6% (1,223)

Forestry 4% (804)

Industrial 3% (709)

Public Health 3% (568)

Figure 1 - Non-crop market by end use ($ million), 2007

AIS.qxp 7/10/08 12:14




sprays are easily the most important invalue. Water dispersible granules,emulsifiable concentrates, wettablepowders, baits, coils, suspension con-centrates, vapour-releasing productsand dusts are among the most widelyused.

800 companies own the registeredbrands, from multinationals to singleproduct enterprises operating in onepart of one country. 15 companieshave sales in excess of $100million/year, with Scotts leading thefield at approaching $2 billion/year.Bayer has over 800 brands, Dow 300,Scotts 400, and Syngenta 900. Storebrands are also significant.

What is behind the growth?Until 2007, most of the world hadenjoyed strong economic growth forover a decade. Over 50 countries sawincreases of over 4%/year in real GDPfrom 1995-2005, compared to just 25in the previous decade. At the level ofthe individual user of pesticides, thistranslated into significant and mostlysustained increases in disposableincome.

What is striking is how many peoplechose to spend part of those increaseson pesticides - to make an improve-ment in the quality of their home envi-ronment. Mostly this has been to con-trol crawling and flying insects. Someof these bugs are just a nuisance butmosquitoes and others are also vectorsof disease like malaria and chagas,hence the need to be rid of them.

Governments in mosquito-endemiccountries have control programmesbut few have made much impact onmalaria, which continues to affectbetween 500 million and 1 billion peo-ple each year. It falls to the ordinary cit-izen to buy and apply pesticides ifthere is to be any real reduction inmosquito problems in the home. Thelast decade has provided an unprece-dented increase in wealth and this isbehind the major boost in demand fornon-crop pesticides.

The other macro-stimulant has beenimproved access to information, via tel-evision, personal computers andmobile phone ownership. This hasenabled the ordinary citizen through-out the world to know more about theproducts available to kill pests andwhere to purchase them.

A combination of more spendingmoney and better information hasextended empowerment to many newconsumers, including the poor andthose in rural areas. The private sectorhas proved effective at expanding the

distribution of insecticides in smallpacks and aerosols to reach remotecommunities, so growth has not justcome from urban consumers.

As yet, however, the commercialresponse from multinational activeingredient manufacturers has beenpatchy. The overall level of commit-ment to non-crop pesticides is notmuch higher than it was ten years ago.

Bayer still has the most seriousengagement, while Sumitomo has anarrower focus but is strong in a fewsegments, such as household insecti-cides. BASF looks capable of addingsignificantly to its involvement but it isunclear whether such a move is immi-nent.

Syngenta, meanwhile, has devel-oped its non-crop business, for exam-ple in relation to vectors, pest manage-ment, lawn and garden, but, lookingahead, non-crop does not appear to bereceiving much additional priority with-in the overall business. For Dow andDuPont, non-crop remains on thefringe.

The increased attention to biofuels,coupled with fears, albeit imaginary,about future shortages of food, hasonce more captured the attention ofsuppliers of inputs to crop agriculture.Promising moves via the GATT andchanges in agricultural policy in manydeveloped countries to shift a largerpart of crop production towards areasof the globe better suited in resourceterms, may be derailed or at leastdeferred. This makes it harder for non-crop protagonists within pesticide com-panies to make the case for a greatershare of investment.

New developmentsProbably the most important singlechange affecting the future of non-crop pesticides has been the involve-ment of the Gates Foundation in aglobal effort to eliminate malaria. Thisis being pursued through two parallelinitiatives: pharmaceuticals (new vac-cines and therapeutic drugs) and bettercontrol of mosquitoes by a dramaticincrease in the use of insecticides.

For the latter, the foundation is ineffect proposing to provide funding onan unprecedented scale to assist pesti-cide companies to develop new activeingredients, exploit existing ones betterand support new formulation anddelivery concepts (such as treated bednets) while also improving the distribu-tion of the resulting products, whichhas often been a serious impedimentuntil now.

The foundation’s initiative has notonly focused attention on the publichealth market, which hitherto has beentoo small to attract investment from themultinationals, but has also stimulatedinterest in other parts of the non-cropmarket. It has drawn attention to a fun-damental choice facing society. Usingpesticides entails risks for users and theenvironment, against which the bene-fits have to be assessed in developingpolicies on what are - and what are not - acceptable uses.

Demonstrating the benefits thatgood use of insecticides can achieve tomake a significant difference to peo-ples’ health is an invaluable counter-balance to those who advocate theextreme precautionary approach topesticides. For decades, the initiativehas been increasingly in the hands ofthose advocating the elimination ofpesticides; true, evidence-based evalu-ation of the benefits as well as the riskshas failed to capture the public’s atten-tion or mainstream political support.

The involvement of the GatesFoundation should redress that bal-ance, although to what extent dependsin part on demonstrating to a confusedpublic that insecticides can offer aresponsible and effective way for manto interact with nature without correla-tive damage.

For example, there has already beena substantial rise in the use of insecti-cide-treated bed nets. The evidence isaccumulating this is making a signifi-cant and lasting impact on the suscep-tibility to malaria of the communitiesadopting them, without affecting theenvironment.

A second new development is theincreasing interest of consumer com-

panies. A look at the shelves of the rel-evant retailers will reveal home pesti-cide products for sale under thenames of SC Johnson, Sara Lee andReckitt Benckiser - assuming, ofcourse, they are not too discreetlytucked away!

These firms and other consumergiants have been in the market forsome years but what is intriguing is therumoured entry of other large con-sumer product companies such asUnilever and Procter & Gamble. Non-crop is very small business comparedto cooking oils and detergents, butthey could be attracted by its record ofgrowth and profitability, as well as itsgood prospects and the ‘fit’ it couldhave with their other brands.

If they become more involved -admittedly a big ‘if’ - companies likethese will be looking for ways to bettersatisfy the needs of consumers in rela-tion to insect and rodent control.Because of their product background,they will be more sympathetic to non-chemical approaches to new productdevelopment.

The outlookA few years back AIS made a projec-tion that the non-crop market wouldbe worth €13-14 billion by 2010 (SCM,January-February 2005, pages 20-21).That estimate was in fact over-cautious,because this figure was reached by2007.

If growth continues at the rate of thelast few years, the non-crop market willbe worth €18 billion by 2010.However, in view of current economicproblems, we incline to the view thatgrowth will continue at around half thatrate for the next two to three years, inwhich case the market will be worthabout €16 billion.

It is a useful reminder to agrochem-icals companies that there are today6.6 billion actual or potential customersfor non-crop products. Even so, atthose projected levels of growth, glob-al average per capita consumption willstill be under 25% of what it is today inmost developed countries, so thepotential is massive.

For further information, pleasecontact:Rod ParkerAgricultural Information Services9 Bovingdon RoadLondon SW6 2APUKTel: +44 20 7371 8913Email: [email protected]: www.aisglobal.net

AIS.qxp 7/10/08 12:14




Me too - but what to do?Nicola Mitchell, managing director of Life Scientific, offers a guide to the EU registration of genericplant protection products

One of the guiding principles of genericproduct development and registration isto work exclusively within the precedent

set by the originator for the reference product.Therefore you should do nothing new or different.This means that the productshould have the same label(copyright-free), a purer activesource, no new impurities, acomparable if not identical for-mulation by reverse engineer-ing and so on.

The comparability of the for-mulation can be confirmed byreference to the originator’sdata package by thecompetent authori-ty. However, the cri-teria used differthroughout Europe.In the UK, forexample, all areas ofthe risk assessmentare part of the com-parability assess-ment, whereas inFrance, historically,only chemistry andtox ic i ty /opera torexposure havebeen considered.

Regulatory strate-gy is obviously verymuch driven by theparticular product and target market but a com-mon approach for Northern Europe would be toregister an identical product in the UK as the ref-erence member state first and nationally elsewherethereafter (e.g. by mutual recognition for Annex Ilisted actives). The steps to take would be as fol-lows.

First of all, you should develop or reverse engi-neer a formulation comparable to, if not identical to,an out of protection (ten years) reference product.Subject to patent status, the development, submis-sion and evaluation of the dossier (if not approval)may proceed before data protection expires.

The ‘identical’ option affords obvious benefits ofaccelerated market access under existing nationalrules (e.g. the UK’s Fast and the French PréparationBis procedures) and later allowing for extrapolation tothe originator’s re-registration Annex III data pack-age. Being additional Annex III data, this attracts noadditional data protection in the UK; for ‘comparable’products, partial extrapolation is still possible.

Secondly, you will need to submit proposed for-mulation composition to Pesticides SafetyDirectorate (PSD) in the UK as phase one of a two-

stage application, for an assessment as to its iden-ticality and so to determine if the complete applica-tion is likely to result in an approval.

Where the PSD response is favourable and theproposed formulation is ‘identical’, you can then

submit the second phase of atwo-stage application by fullextrapolation to the origina-tor’s data package, precludingthe need for new ‘me-too’data.

Where the PSD response isnot favourable and the pro-posed formulation is ‘compara-ble’, the next step is to submit

the second phase of two-stage application by par-tial extrapolation to the originator’s data packagetogether with bridging/confirmatory data on the‘me-too’.

Reference product characterisation The registration objective for a generic/establishedproduct remains the safety of humans, domesticanimals, livestock, wildlife and the environmentgenerally, as well as efficacy. The term ‘generic/established’, as applied to a product implies aprecedent, i.e. the product has already been evalu-ated and authorised and its properties are wellknown and widely documented.

Therefore, the registration process is more aboutdemonstrating comparability to the referenceproduct than about establishing safety from firstprinciples. For this reason, an understanding of thereference product is essential.

This includes an evaluation of the regulatory sta-tus (which reference product, which legislation,what stage of the EU review, is it Annex I listed?),data protection, the data package (for gaps), itspatent status (manufacturing process, combina-

data’ national and EU mutual recognition re-regis-tration applications.

In conclusion, therefore, generic registration isall about gaining a thorough understanding of theprecedent/reference product and levering thisprecedent by working within it and developingidentical products, conducting well designed bridg-ing/confirmatory studies and developing well rea-soned scientific rationale for extrapolation of exist-ing data, and thereby providing for acceleratedmarket access.

tions, formulation), commercial status (extant orwithdrawn), safety status (e.g. NPEs) and field ofuse (foliar, soil, seed treatment), plus all availableinformation sourced from the competent authori-ties, commercial and proprietary databases - and,for that matter, the industry grapevine.

The greater the extent to which the referenceproduct can be characterised, the greater theprecedent that can be leveraged and the faster andsimpler the registration process. The ability toreverse engineer an identical formulation is pivotalhere. It allows for both access to protected markets,including Germany, via new parallel import rules,and accelerated access elsewhere, and extrapola-tion to full Annex III data (no protection) and ‘no

For more information, please contact:Life ScientificUnit 6Courtyard Business CentreOrchard LaneNewton ParkBlackrockCounty DublinRepublic of IrelandTel: +353 1 283 2024E-mail: [email protected]: www.lifescientific.com

Life.qxp 7/10/08 12:14

Over 2,000 chemical, printing and electronicscompanies are working on the next evolutionof electronics: printed electronics. This enableslighting, displays, circuits, solar cells, sensorsand other components to be laminar, cheaper,flexible, robust and even in some casestransparent. They can be printed or partiallyprinted and made in high volumes, large areasand be much lower cost than conventionalelectronics.

Printed electronics is enabling new productstoday, from lower cost solar cells to e-bookssold by Amazon and Sony. It is the chemical

industry that has the most to gain from thisemerging technology, due to therequirement for specialised, high valuematerials such as printable semiconductors.Others are working on replacement materialsto rare or precious metals needed forconductors, and others again on newsubstrates and encapsulation techniques.There is huge scope, needs and opportunity.For more information IDTechEx is hostingthe biggest event on the topic – PrintedElectronics USA 2008 – controversially inthe heart of the silicon world – in San Jose,CA, on December 3-4.

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IDTechEX.qxp 7/10/08 15:09 Page 1


Water treatment chemicals


Dr Elizabeth Milsom outlines the Royal Society of Chemistry’s recent report on sustainable water

Chemicals & the future ofwater

Securing a sustainable water supply in the light of climatechange, massive population growth and man-made pol-lution will be one of the biggest challenges for global

communities in the 21st century. Our demand for a clean andsafe water supply is increasing with our rising population;water treated to an appropriate standard is required not onlyfor drinking but also to satisfy all our domestic, industrial andagricultural needs.

The charity Water Aid estimates that one in eight people donot have access to safe drinking water and over 40% of theworld’s population does not have adequate sanitation. Even inthe UK, pressure is being put on our water and sewerage sys-tem as the population around London increases and changingweather patterns mean that more instances of flooding anddrought are likely. We are going to need to do more with fewerresources, for which good water management will be essential.

The regulatory framework Sustainable water management must take place within exist-ing and future regulatory frameworks. The EU’s WaterFramework Directive (WFD) was adopted in 2000 with thegoal of ensuring clean, sustainable water supplies in the EU.

The WFD aims to achieve ‘good status’ for all groundwater,rivers, lakes, coastal and other water bodies throughoutEurope. The term ‘good status’ is based upon the ecological,chemical and physical aspects of these bodies of water. Tomeet these requirements will require chemistry, both for theanalysis of the status of water resources and for remediationmeasures.

The Royal Society of Chemistry (RSC) is the UK’s profes-sional body for chemical scientists and an internationallearned society for advancing the chemical sciences. LastDecember it launched a report by industrial and academicexperts called ‘Chemical Science Priorities: Sustainable Water’.

This aimed to address the problems of sustainable waterover the entire hydrological cycle (which describes the contin-

uous movement of water on, above and below the surface ofthe Earth). It highlighted eight key chemical science chal-lenges and each chapter made a series of recommendationsto enable the chemical sciences to deliver the technologies,infrastructure, skills and stakeholder education for a sustain-able water supply.

The chemical sciences already play an important role inevery aspect of the hydrological cycle and will play an evenlarger role in sustainable water management in the future. Forexample, scientists will have an important role in understand-ing and predicting the impact of climate change, which willinform decision makers about future water supply and flooddefence infrastructure.

Potable water treatmentIn Chapter 3 of the report, Professor Simon Parsons, Dr BruceJefferson and Dr Noel Christopher of Cranfield University out-line the role of the chemical sciences in the treatment of waterto both make it drinkable and also to remove contaminantsfrom wastewater and industrial waste streams.

Chemistry plays a major role in all aspects of water treat-ment and supply, from allowing us to characterise sourcewater quality, including quantifying pollutant load, to remov-ing particles and organic and inorganic pollutants, providing adisinfectant residual and controlling water quality in the distri-bution system.

Processes for raw water treatment are in excess of 100years old. Most operations include coagulation followed bysedimentation to remove suspended solids and bulk organics,then filtration and finally disinfection.

The characteristics of the particles, such as their size, shape,density and charge, are critical factors in designing an effec-tive process. An effective sedimentation process can removemany particles, but negatively charged colloidal particles thatcause turbidity require a chemical coagulant process for effec-tive removal.

A research challenge, therefore, is to develop coagulantsthat deliver effective performance but produce minimal solidresidues. Additionally, research is needed to produce highcharge coagulants at neutral pHs and new ideas for coagulantrecovery and reuse.

Filtration through sand has been used effectively for manyyears to remove particulate material in water, including claysand silts, micro-organisms and precipitates of organics andmetal ions. The process is based on particles colliding andsticking to the sand as the water flows past.

Recent developments include novel filter media and, mostsignificantly, membranes. Membranes are effective at remov-ing key colloidal material as well as pathogenic organisms,such as cryptosporidium. However, they are prone to foulingand this is a key developmental challenge. Activated carbon iseffective at removing natural organic matter and colour, pes-ticides, taste- and odour-forming compounds and algal toxins.

Ozonation followed by activated carbon is the UK industrystandard for pesticide removal. Ozone breaks down pesticidesinto compounds that are readily absorbed by the activated

Water storage inice and snow

Water storage in the atmosphere

Precipitation

Snowmelt run-offto streams

SublimationEvapotranspiration

Surface run-off

Water storagein oceans

Evaporation

Condensation

Streamflow

Evaporation

Ground-water storage

SpringFreshwater

storage

Infiltration

Ground water discharge

The natural cycle of water

RSC.qxp 7/10/08 12:15




carbon. However, ozone processes can produce a potentiallycarcinogenic bromate by-product. This has led to the devel-opment of photochemical processes, such as UV andadvanced oxidation processes, although these can also createharmful by-products.

The whole treatment chain contributes to the removal ofbacteria, pathogens and viruses. The addition of chlorine, oranother suitable disinfectant, is the final part of the treatmentprocess.

Chlorine is the most commonly used disinfectant becauseit is relatively cheap and the water industry is confident usingit. However, ozone is the disinfectant of choice in many partsof Europe and UV light is already used extensively on goodquality groundwaters. Both chlorine and ozone can produceundesirable disinfection by-products and both ozone and UVare energy-intensive.

Chloramination (i.e. dosing a controlled amount of ammo-nia after chlorination) has the advantage of providing alonger-term residual in the distribution system and overcom-ing the taste problems associated with excess free chlorine.However, it can produce an undesirable by-product and cangenerate a bad taste if the mistake is made of mixing chlo-raminated water with water containing residual chlorine.

Energy makes up 34% of the costs of producing potablewater. Energy savings are possible through better manage-ment and operation of the water treatment works. However, ifnew regulations require additional treatment processes to beinstalled or if the quality of the raw water deteriorates, energycosts are likely to increase.

Key future challenges for suppliers of water include scarci-ty, the need to treat poorer quality water and energy usage.Water scarcity will lead to increased interest in energy-inten-sive desalination and water reuse and recycling; these sourceshave a wider range of contaminants that require treatment.Microfiltration and reverse osmosis technologies are expectedto be important in treating poor quality water.

Wastewater treatmentOnce water has been consumed, used to wash our clothes ordishes, it enters the sewerage system, where it needs to betreated once again. The principle function of wastewater treat-ment is to remove solid, organic and microbiological compo-nents that cause unacceptable levels of pollution to the receiv-ing water body.

All wastewater treatment facilities have compliance stan-dards to meet in relation to biological oxygen demand andsuspended solids. Additional consideration is given to ammo-nia, nitrate, phosphorus, micro-organisms, specific organicpollutants and metals, depending on the size of the treatmentfacilities and the nature of the discharge.

The processes most commonly encountered in wastewatertreatment include screens, coarse solids reduction, gritremoval, sedimentation, biological treatment and filtration.The majority of the processes work through the application ofa physical force and are collectively known as physicalprocesses.

The other processes operate through a biological reactioncoupled to an adsorption step. Here, micro-organisms usecomponents as part of their growth cycle and convert dis-solved organic components to solids for removal in down-stream physical processes.

The two key areas of continuing concern to the industry areenergy and sludge. Energy comprises around 28% of theoperating cost of treating wastewater. Here too, savings arepossible through better management practice but they will bedifficult to sustain if the trend towards ever lower allowable

limits of components continues. In this scenario, innovation isthe only pathway to sustained long-term savings.

Sludge makes up around two thirds of the total costs ofwastewater treatment and is a key area where the use ofappropriate chemicals and chemical processes can greatlyenhance performance and sustainability. However, currentunderstanding of such systems is limited and is the criticalbarrier to improvements. Consequently, the treatment anddisposal of sludge is potentially the area where chemistry canhave the greatest short term impact.

Chemistry will play an increasingly important role in waste-water treatment. Traditionally its main focus has been on ana-lytic techniques to aid the engineer in understanding the bio-logical and physical processes utilised. In the future, the needto remove more exotic components will result in a greateremphasis on chemical processes.

In particular, chemistry will have to provide solutions for theneed to reduce nutrients to very low levels and remove dis-solved metals and specific organic compounds, such asendocrine-disrupting chemicals. This will come from both animproved understanding of the nature of pollutants, and thedevelopment of innovative technologies to remove such com-ponents.

The most likely areas for development in the short to medi-um term are new adsorbents, new sludge-conditioning chem-icals and technologies and chemical oxidation technologiesthat can target specific compounds rather than deliver blanketsolutions.

Industrial water treatmentIndustrial water treatment is dominated by the use of wateras a heat transfer or process medium. Heat transfer is eitherin the heating/steam-raising mode or as a cooling medium.Therefore the challenges are to minimise corrosion of the

Reservoir

Coagulantadded

Flocculation tank

Sludge collector

Filtration

Filtered waterstorage

Disinfectionand

fluoridation

Distribution

Sludge thickener

Sedimentation basin

Horticultural landfill

The water treatment cycle

RSC.qxp 7/10/08 12:15




plant and distributing pipe-work, the deposition of waterhardness salts and bacterial fouling of the plant.

There is also a challenge to ensure maximum heat transferand to minimise environmental impact together with healthand safety issues, particularly the impact of legionella andrelated public health issues. The process applications of waterare wide and diverse, ranging from a solids transfer mediumin paper production to a solvent and lubricant in engineeringcutting fluids.

There are opportunities to reduce water use in such appli-cations. Advanced vessel and pipe coatings will aid waterreduction and recycling by reducing the amount of productthat sticks to vessel walls and pipes, resulting in less productloss and lower water requirements for cleaning.

Chemical contaminantsHuman activity has also resulted in the emergence of chemi-cal contaminants in the environment, which are typicallymobilised by water. Further research is required to understandthe fate and environmental risk of emerging contaminants -including new pharmaceuticals and nanoparticles, to namebut two of them.

The study of these contaminants requires the developmentof advanced monitoring technologies, such as advanced sen-sors, to provide real-time information wirelessly on water qual-ity and any pollution events.

However the best form of cure is prevention and the ulti-mate goal for the chemical sciences is to design products thatare not only highly effective in their use but which alsodegrade to harmless products on reaching the environment.Here, too, chemistry will have a very important role to play.

Green chemical technologyGreen product design extends the principles of green chem-istry to the use of products and their ultimate disposal. Thisincludes the design of highly functional products that are effi-cacious in their intended use but possess little or no risk tohuman health or the environment and biodegrade rapidly.These are also some of the key principles of REACH.

Chemists are now beginning to use SAR models to predictthe activity and environmental behaviour of chemicals and tooptimise performance on both criteria. This approach offersopportunities to optimise and minimise end of pipe treatment,particularly with respect to achieving WFD objectives.

In addition to designing products that have minimal envi-ronmental impacts at end of life, it is also possible to designproducts with reduced impact, either in terms of water vol-ume use, or potential impact on water that minimise waterand energy use during their use phase.

Future work Following on from the launch of the report, a water expertworking group was formed. This is made up of individualsfrom the water industry, academia, other learned organisa-tions and the RSC’s own Water Science Forum, in order totake forward the reports recommendations.

Important areas of current work include investigating greywater standards, new analytical water monitoring methods,and new chemicals and processes for water treatment. Thechemical sciences have already played an important role inwater management. This, coupled to a good policy at EU andnational level, will be essential if we are to secure a clean andplentiful water supply for future generations.

For more information,please contact:Dr Elizabeth MilsomEnvironment & EnergyPolicy ManagerRoyal Society ofChemistryBurlington HousePiccadillyLondon W1J 0BAUKTel: +44 20 7440 3395E-mail: [email protected]:www.rsc.org/water

Chlorination. Sulfonation.Methylation.

CABB GmbH

Am Unisys Park 165843 Sulzbach am TaunusGermany

Phone +49 6196 757-8780Fax +49 6196 757-8909

[email protected]

RSC.qxp 7/10/08 12:15

Project1 7/10/08 12:27 Page 1




The whole packageChemicals are increasingly used as part of wider water treatment systems. Sean Milmo reports

Sales of water treatment chemicals are projectedto grow strongly in the medium term, ahead ofthe rate of increase in GDP in many parts of the

world. However, sales of physical and mechanical sys-tems for providing clean water and enabling water tobe used more efficiently are growing at an even fasterrate.

The US-based market research organisationMcIlvaine reckons that sales of water and wastewaterchemicals will rise by an average of 5%/year in theperiod 2008-2012, with the highest growth of aroundan average 8%/year being in Asia. McIlvaine also esti-mates that the world market for large-scale reverseosmosis (RO) systems will expand by almost 50% overthe next four years, equivalent to about 12%/year.

The difference in the growth rates between chemi-cals and systems shows the changes of technologies inwaste water treatment, particularly in the industrial sec-tors. There has been a shift from traditional processesdominated by chemical applications to ones in whichengineering plays a much bigger role.

For chemicals companies, there are still opportuni-ties for establishing niches in chemical treatmentthrough new products, but there are even biggeropenings for the development of innovative materialsfor water regeneration, recycling and other systems.Even processes centred on bioremediation need high-ly efficient filtration and membrane materials.

Industries across the world are having to invest inmore efficient wastewater technologies because of thepressure on water resources caused by economicdevelopment, rising populations and urbanisation. TheUN has forecast that two thirds of the world’s popula-tion will have to endure water shortages by 2025. For1.8 billion people, the scarcity will be severe.

Statistics from the UN’s Food & AgricultureOrganisation demonstrate that there are plentiful sup-plies of freshwater which fall from the sky into rivers,lakes and aquifers. The trouble is that these suppliesare not evenly distributed, so that sparsely populatedareas have abundant water while, in heavily populatedurbanised regions, availability is inadequate.

Water is hugely expensive and inefficient to trans-port. Even in water-rich countries, large amounts leakfrom pipeline networks. The imbalance in supplies isaggravated by widespread pollution, which is usuallycaused by industries, such as textiles, paper, food andagriculture, consuming large quantities of water.Contamination has made the availability of drinkingwater even scarcer.

Access to plentiful clean water is beginning to giveregions and countries a big economic advantage inworld trade. Industries with abundant water availableclose to hand can export crops, products and manu-factured goods in the form of ‘virtual’ water to areasstruggling with water scarcity.

The vital need for clean water is underpinned byincreasingly restrictive regulations on water pollution indeveloped countries and also in emerging economies.

In China, which is afflicted with water scarcity in manyareas, many manufacturing plants have recently beenclosed down because they have breached tighter ruleson wastewater emissions.

“China’s latest Five Year Plan requires every city witha population of over 500,000 to treat 60% of itssewage by 2010,” says Alan Dimery, head of the watertreatment business at Ciba Specialty Chemicals.

In addition to complying with tougher environmen-tal legislation, some industries are also having to adaptto new process technologies that require the use ofultra-pure water (UPW). These sectors range frompower generation to electronics and pharmaceuticalsproduction.

Environmental and technological pressures havestimulated the development of new technologies inwater treatment and reuse, which, in many cases,operate within integrated systems based on differentforms of filters and membranes. These systems arecombined with more sophisticated types of chemicalprocesses, like ion exchange, electrodeonisation, acti-vated carbon and applications with nanoscale sub-stances and particles.

Ion exchange is now being introduced in a widerrange of industries because of its ability to eliminatespecific kinds of pollutants and impurities as well as toregenerate particular components of a water process.

“The strength of ion exchange is its flexibility,”Professor Wolfgang Hüll of the Institute of TechnicalChemistry in Karlsruhe, Germany, told a recent ionexchange conference organised by the Society ofChemical Industry (SCI) at Cambridge, UK. “No mem-brane can be as selective as ion exchange can be,” headded.

Most standard ion exchangers involve the use ofresins containing a relatively small range of organic,usually polymeric, chemicals. “These resins cover theneeds of the majority of applications in water andwastewater treatments and further applications,” saidHüll. “But the standard exchangers are often not selec-

tive enough for the elimination or concentration of cer-tain target components like heavy metals, nitrate,boron, arsenic, fluoride, lithium and other species.”

A number of polymeric exchangers have beenintroduced for the sorption of heavy metals, nitrateand borates, while inorganic materials are also beingused to eliminate certain pollutants. Novel inorganicexchangers include ferrocyanides, titanates, zirconiumphosphates, metal oxides and aluminium tungstate.

Among the chemicals companies which are bene-fiting the most from the changes in water treatmentprocesses are producers of high performance poly-mers. These can be required for more effective con-ventional chemical treatments like polymeric floccu-lants, as well for ion exchange resins.

Polymers are also the key material in filters andmembranes, particularly those using RO. They notonly provide the structure of the filter or membranebut can also have chemical properties for the separa-tion or immobilisation of substances within effluents.

Chemicals companies with competences in poly-mers for both material and chemical applications areable to establish key positions in the water treatmentsector. Dow Chemical, a major producer of filtrationand membrane materials and ion exchange resins, ispoised to become an even stronger player after thecompletion of its takeover of Rohm and Haas, whichis a key producer of speciality ion exchange resins.

Companies like Dow are well placed to take advan-tage of the rapid growth in the construction of desali-nation units to provide water for both drinking andindustrial use in areas of water scarcity.

Despite their high energy costs capital expendi-ture on desalination projects has been increasingacross the world by an average of 18%/year over thelast three years, according to Global Water

Ion exchange resins are widely used in watertreatment

Milmo.qxp 7/10/08 12:15




Intelligence. The growthrate is expected to

slow to around10%/year but willstill amount toover €4.2 bil-lion/year in capitalinvestment, while

total operating costs willbe around €5.7 billion/year.

In China the governmentis now supporting desalina-tion as a national high-techindustry. Because of controls

on the abstraction of surface andgroundwater, industrial projects in coastal areas,including power generation, will have to rely ondesalination.

Most desalination technologies are based on thethermal evaporation or distillation of seawater or onmembranes that imitate the natural biological processof osmosis. In addition to producing water comparableto fresh water, desalination plants also discharge efflu-ents with a high concentration of brine and other con-taminants, including a range of chemicals used in theprocess.

RO membrane systems based on polymer materi-als are taking market share away from thermal desali-nation methods, so RO should account for most of theexpenditure on new plants in the sector by next year.Besides having lower capital costs and requiring lessenergy, RO is also more efficient at removing microor-ganisms and many organic contaminants.

One major disadvantage has been that RO’s saltremoval has not been so effective so that the water itproduces has more salt than that provided by thermaldistillation - typically 500 ppm against 25 ppm,according to a recent study by the Pacific Institute inOakland, California. However advances are beingmade to lower costs, boost productivity and raisedesalination efficiency, particularly through the use ofimproved or different polymers.

“The key issue with reverse osmosis is throughput,”explains Scott Noesen, sustainability director at Dow,which is aiming to reduce RO costs by 35%. “If we canget more throughput at lower pressure, we can lowerenergy costs, because the higher the pressure, thehigher the need for energy. That is what we are focus-ing on. The design and structure of our membraneenables them to operate at lower pressures becausethe polymer resins are more robust.”

RO membranes are vulnerable to blocking bymicroorganisms and to damage by chemicals.Therefore, salt water has to be pre-treated. In manycases chlorine is used to eliminate microorganisms butthen the chlorine has to be removed to avoid harmingthe polymers in the membrane. Recently researchersin Korea and Texas have developed chlorine-resistantpolysulphone-based membranes as alternatives topolymers like polyamide, which is particularly suscep-tible to chlorine.

Among other deposits which can paralyse both ROand thermal distillation systems is limescale, which isformed as a result of salt dissolving into carbonate andhydroxide. BASF is a major supplier of scale inhibitorsto desalination operators. These comprise long-chain

polymers, like modified polycarboxylates, with a neg-atively charged strand which prevents the forming ofcrystals.

Successes with combinations of filtration and mem-brane systems, often backed up by highly specifictechnologies like ion exchange and activated carbon,have led to their introduction in the textiles sector.Some textile mills and dye houses have been strug-gling for years to reduce their emissions, particularly ofdyestuffs, to acceptable levels.

The need for greater water efficiency is a matterof urgency for textile manufacturers in areas ofwater shortages or in regions where the regulatoryauthorities are making zero discharge of liquidwaste compulsory. The global average for dischargeof waste water in textile production is 100-500litres/kg of fabric.

Conventional water treatments in textiles use oxi-dation through the application of substances likeozone, hydrogen peroxide and ferrous sulphate or viaelectrochemical systems. They also apply coagulantsand flocculants based on alum, lime, ferrous sulphateand ionic polymers.

The adoption of filtration and membranes in themanagement of textiles waste waster is becomingmore widespread. Nanofiltration using polyamide,polysulphone and polyester membranes has shownitself to be highly effective in the removal of reactivedyes and electrolytes used in the dyeing of cotton. Dyeremoval rates have been as high as 99.9%.

Polymeric ion exchange resins are efficient at sepa-rating reactive dyes with an uptake capacity of around0.91 gm/gm of polymer, researchers from IstanbulTechnical University told the Cambridge conference.Polymers in the form of wetted gel also interact wellwith dyes.

Integrated systems incorporating ultra-filtration andRO are helping textile mills achieve zero discharge ofwaste water through the recycling of water, the reuseof materials and the incineration of the remaining solidresidues.

Benninger, an Austrian textile machine manufactur-er which has expanded into water management, hasdeveloped a system comprising an ultra-filtrationdiaphragm and RO membranes. The ceramicdiaphragm, which is resistant to chemicals, holds back

particulates, chemicals and long-chain organic sub-stances that could damage the polymer RO unit whichdissolves dyestuffs and salts.

At least 80% of the waste water is recycled, whilechemicals like caustic soda and size components arerecovered for reuse. The remaining concentrates arethickened and solidified through evaporation tech-niques for incineration with a heat recovery level of70%.

Integrated water recovery technologies, bringingtogether ultra-filtration, RO and ion exchange process-es, are being applied in the electronics industry whichis a big consumer of water and also needs UPW.Other sectors needing UPW, such as power genera-tion, food, beverages and non-woven textiles, havestarted to use ion exchange and other interactiveproperties to purify the water coming into the manu-facturing plants.

Argonide of the US has developed a non-woven fil-ter medium consisting of nano-alumina fibres of only2 nm in diameter which attract and retain particles byelectrostatic forces.

When packed into a 6.35 x 25.4 cm cartridge, thefibres comprising the mineral boehmite provide morethan 10,000 m2 of active surface area. A majoradvance made by Argonide’s nanofibre is that it is ableto achieve a high flow rate with an increased retentionrate of particles and mircroorganisms and with a dropin pressure.

“This technology represents a breakthrough inmaterial science that synergistically combines the bestaspects of charged and mechanical filtration in onemedium,” says Rod Komlenc, vice president of busi-ness development at Ahlstrom Filtration, which haslicensed the technology from Argonide.

The system’s comparatively large pores providehigh flow at low pressure drop. Meanwhile, its largesurface area and electroadhesive charge enable it tobe chemically modified to create affinity with specificcompounds, Komlenc adds.

Nanomaterials like this have the potential for thesame flexibility as ion exchange. Similar break-through technologies in water treatment are likely tobe developed in the short to medium terms asindustries across the world confront the acute needto conserve water.

Membrane skid (above) & membranes from Dow (top left)

Milmo.qxp 7/10/08 12:15




IDA resins: VersatilespecialistsDr Stefan Neumann of Lanxess looks at a selective ion exchanger for handling heavy metals

Transition - or heavy - metals play a key role in many tech-nical processes, but they are often found only in very lowconcentrations that make processing difficult, for example

in wastewater, as catalyst residue in a product or in the miningof low concentrate ores.

Transition metals such as lead, cadmium, cobalt, copper andnickel are valuable and rapidly diminishing raw materials. Thedecreasing availability and rising prices of raw materials are forc-ing industry to search for efficient methods of finding newsources, minimising losses and increasing purity.

Conversely, these metals possess toxic properties that adverse-ly affect both human health and the environment, and thesetherefore need to be removed from wastewater, groundwater anddrinking water. The use of special ion exchangers that can selec-tively bind and concentrate these offers interesting potential inboth ways. Not all ion exchangers are suitable, however.

Selectivity the key‘Normal’ ion exchange resins that are primarily used to softenwater via the adsorption of Ca2+ and Mg2+ ions are usuallyunsuitable for the adsorption of heavy metals because the func-tional groups responsible for adsorption are normally sulphonicacids or salts that bind metal ions mainly via electrostatic inter-actions and therefore exhibit only limited selectivity. Therefore,traces of nickel ions would be adsorbed onto these resins, butwould then be displaced quickly by other ions present in thematrix at a much higher concentration.

Nevertheless, some resins can offer very high selectivity fortransition metals. These have been around since the 1960s buthave previously been hugely overshadowed because 70% of allion exchange resins are used to soften water. Such resins, likeLanxess’s Lewatit TP 207 and 208, are highly selective, due totheir chelating anchor groups.

The functional groups responsible for binding metal ions tothese resins are immobilised iminodiacetic acids (IDAs). Thesehave three binding points per anchor group via three interlinkedligands - the two acid groups and the free electron pair of theimino nitrogen (Figure 1).

This causes a strong entropic effect. Once bound, the metalhas to break away simultaneously from three binding pointsbefore it can be desorbed. Furthermore, the bond is created bycomplex chemical mechanisms as well as by electrostatic forces.For example, nitrogen can interact with the d-orbital transitionmetal ions via its free electron pair.

Because of this, IDA resins show an extremely selectiveadsorption effect on all metal ions with suitable electron struc-tures - in particular, heavy and transition metals. In completecontrast to conditions found with ‘conventional’ ion exchangers,the binding of alkali metals, such as sodium or potassium, thatdo not have ‘docking points’ for this lone pair is much poorer

Chelating IDA acids bind metal ions much better than classicion exchangers like monodentate sulphonic acids, which canonly achieve this with difficulty, if at all. Earth alkali metals, suchas calcium and magnesium, are bound by IDA groups via acomplex chemical interaction. Although these bonds are signifi-cantly stronger than for alkali metals, they are still weaker thanthe bonds for heavy metal ions.

IDA resins are therefore able to extract even the smallest con-centrations of, for example, copper, nickel or lead ions from 30%brine solutions. The bond established with these is so strong thatthey can no longer be displaced by sodium ions or others.

This capability makes IDA ion exchangers, also known as‘selective resins’, attractive candidates for handling extremelylow concentrations of heavy metals in a wide range of matri-ces. Residual concentrations of <10 µg/litre are technicallyviable.

These resins are also economical to use, due to their normal-ly high uptake capacities and the long periods between regen-eration cycles associated with this. For example, filters for sepa-rating nickel from drinking water can achieve a service life of upto 20,000 hours in continuous operation.

As heavy metals are involved in many areas of technology,IDA resins are suited to a wide range of applications throughoutthe entire value chain. For this reason, selective resins seem torepresent - paradoxically and yet justifiably - a universally appli-cable product.

Application areasA key application is in the extraction and cleaning of metals.The demand for technically interesting metals is growing, whilethe amount of ores with high metal concentrations is decliningrapidly. Consequently, mined ores often need to be concentrat-ed before they can be isolated in a further process.

IDA resins are an ideal auxiliary product for this. Unlike con-ventional liquid extraction media, they can process solutions withlow concentrations of metal and high suspended substance con-tents. IDA resins can be used to produce concentrations inranges of up to several percentage points.

SO3Na

CCH2

N

CH2 C

O

O

CH2R O NaO Na + Me2+

CCH2

N

CH2 C

O

O

CH2R O NaO Na + 2Na+Me

H2C N

CH2–CO–ONa

CH2–CO–ONa

Ba2+>Pb2+>Sr2+>Ca2+>Ni2+>Cd2+>Cu2+>Co2+>Zn2+>Fe2+>Mg2+>Mn2+>Alkalis>H+

Earth alkali metals Heavy metals Alkali metals H+> > >

Fe3+>Cu2+>H+>Hg2+>Pb2+>Ni2+>Zn2+>Cd2+>Co2+>Fe2+>Mn2+>>Ca2+>Mg2+>Sr2+>Ba2+>>>Alkalis

Heavy metals > Earth alkali metals >>> Alkali metals

H+

Figure 1 - Binding points ofLewatit TP 207

Figure 2 - Order ofselectivity of ion exchangers

Lanxess.qxp 7/10/08 12:16




Their high affinity for copper, nickel, cobalt and other metalsalso makes it possible to extract them from the wastewater ofmining plants, especially leachate from slag heaps and/orresidue deposits. A reference project in one of the world’s largestcopper mines, in Bor, Serbia, recently provided compelling evi-dence of the cost-efficiency offered by this process.

Another area of application in the mining industry is the sep-aration and cleaning of metals. For example, IDA resins can beused to remove troublesome traces of copper from nickel con-centrates.

The broadest application area for IDA resins is in the finepurification of educt and product streams. Within this area,the most widely used process is is the softening of brine streams(30% NaCl) during chlorine production.

In this application, selective ion exchangers protect the sensi-tive membranes in the electrolytic cell against the blockingeffects caused by calcium and magnesium. Any aluminium andnickel ions present in the brine’s raw materials can also beremoved reliably in this process.

Products in the food industry can also contain heavy metals,such as copper finding its way into wine via pesticides. Accordingto the German Federal Environment Agency, levels of lead inredcurrant juice often exceed legal limits. Nickel has also beenfounds in process streams from the sugar industry.

The use of IDA resins in these areas has already been inves-tigated in the laboratory and has also proven itself in a numberof practical cases. In these applications, the ion exchanger onlyremoves unwanted heavy metals, leaving the product otherwiseunaffected.

IDA resins can also be used in recycling product streams.The electrolytes used for surface coating in galvanisationinevitably become contaminated during use. For example, cor-rosion processes cause iron ions to become concentrated in thezinc electrolyte used when coating sheet steel with zinc.

Figure 3 shows how Lewatit TP 207 ion exchange resins havebeen uses in this application. As IDA resins exhibit greater selec-tivity towards trivalent iron than zinc, they can extract iron ionsfrom the zinc solutions galvanisation baths, feeding the reusableZn2+ and Ni2+ back into the process. As a result, the electrolytesare continuously cleaned, enabling the quality of the zinc coat-ing to be maintained constantly at a high level. Costly prepara-tion and disposal procedures for used zinc solutions alsobecome redundant.

A further example of cost-effective recycling in productstreams is the recovery of cobalt from solutions produced dur-ing the manufacture of coatings containing it. The concentrateproduced after the regeneration of the ion exchanger can be fedback into the process. This prevents the contamination of waste-water and minimises the loss of reusable materials.

IDA resins can be used in purifying wastewater streamscontaining heavy metals in detoxification plants. The central

process involved here relies on chemical precipitation caused byadding lyes and/or sulphides.

However, it is sometimes difficult to ensure that heavy metalemission values are not exceeded when using this method.Challenges include the interactions between ions, the high lev-els of residual solubility for some metals and the formation of sol-uble hydroxy and other complexes if insufficient dosages of theprecipitant are used.

Adherence to limits can be ensured when IDA resins are usedafter the precipitation stage. What are known as ‘final exchang-ers’ or ‘police filters’ also work, expecially if toxic sulphides arenot used in the precipitation stage.

The process can be set so that environmentally friendly earthalkali and alkali metals are not retained and regeneration mate-rial from the ion exchanger can then be fed back into the pre-cipitation stage. If wastewater contains only one heavy metalcontaminant (as is the case in the PCB industry, with copper), theconcentrate can be fed back into a galvanic recovery process asappropriate.

Processes used in the purification of groundwater includethe ‘pump-and-treat process’. This involves bringing pollutedwater to the surface, treating it and then pumping it back under-ground. IDA resins are ideal for treating water that is contami-nated with, for example, traces of heavy metals such as nickel,cobalt, zinc, cadmium or lead.

Again, only the harmful substances are selected for adsorp-tion, with the remaining components of the water and its pHvalue remaining unaffected. Results from an extended efficacytest, recently carried out under the supervision of the GermanFederal Environment Agency, show that nickel, for example, canalso be removed efficiently and cost-effectively from drinkingwater using IDA resin without adversely affecting the quality ofthe water.

Development continuesThis article can only provide a brief overview of the diverse rangeof applications for IDA resins that exist today. Others are sure tobe added over the years ahead and product development workis ongoing.

Lanxess’s own IDA resins are being developed in differentgrain-size grades to optimise them even further for various appli-cation areas. Further developments will include looking at mod-ifying the internal structure of the resin by altering the polymerstructure and degree of substitution so as to accelerate the kinet-ics of the exchange procedure or to enable selectivity to be seteven more precisely. Working on customer-specific services willalso increase.

s>H+

2+>>>Alkalis

als

H2O2

Recycledelectrolyte

Zn 2+

Ni 2+

Zn/Nielectrolyte,pH = 3.5

e-

SelectiveTP207

IX

Waste water

Regenerants:H2SO4, NaOH, H2O

Zn/Ni-coatedFe – coil

Zn 2+

Ni 2+

Fe 3+

Zn 2+

Ni 2+

Fe 3+

rawFe - coil

–+

e-Fe

Zn/Ni

For more information,please contact:Dr Stefan NeumannTechnical MarketingManager - Catalysis &Chemicals ProcessingBusiness Unit IonExchange ResinsLanxess DeutschlandGmbHTel: +49 214 30 66243 E-mail:[email protected] Website:www.lewatit.com

Figure 3 - Process flow ofzinc-coating of sheet steel

Quality check on ionexchanger at Lanxess

Lanxess.qxp 7/10/08 12:16


Cosmetics & personal care


A different formulaDistributors play a role that goes way beyond simple distribution in the personal care industry.Ahead of SCS Formulate, we interviewed some of the key UK players

The personal care market is one where distribution plays arole that is far from confined to simple distribution as it isnormally practised in the chemicals industry. The sheer

complexity of the ingredients involved in cosmetics, the rapidlychanging product range available and the diversity of end useapplications combine to make this inevitable.

Even the largest players in chemical and botanical productsfor personal care are liable to have multiple representationacross the different national markets in Europe. That much isobvious from a glance around the show floor at any major per-sonal care event. At the very largest, In-Cosmetics, they are verymuch in evidence. At national events, they are dominant.

One example is the Society of Cosmetic Scientists’ Formulateconference and exhibition. This is the key UK event for formu-lators, where many of the product innovations are launched.Ahead of its return to the Telford International Centre onNovember 18-19, we asked some of the UK distributors fortheir take on the state of the market. Those replying were thefollowing, with their principals listed in brackets:

• Scott Davison, marketing manager at Univar Europe (BASF,Amerchol, AAK, 3M, Cabot, Huntsman, Kao and Kolb, plusan in-house colour business called Univar Colour)

• Brian Nevin, marketing manager at Surfachem (Stepan,Shell Chemicals, Lubrizol Advanced Materials, EvonikIndustries, Dow, Rhodia Novecare, P&G, Prayon, Schill &Seilacher, Kerry Bioscience, Gulbrandson, Roquette, Granulaand Himar Speciality Chemicals)

• Gillian Berry, group marketing manager at S. Black (MerckKGaA, Dow Corning, AkzoNobel Surface Chemistry PersonalCare, Inolex, DSM Pentapaharm, Lipotec, Provital, Elementis,Beraca, Miyoshi Kasei, Sasol and Sun Chemical)

• Natalia McDonagh, group marketing manager at Cornelius(BASF, Lonza, Strahl & Pitsch, Phoenix, RITA, ChemicalCompounds, Buntech, Jeen, Innospec, Silab and Huber)

Do you regard your company as essentially adistributor or more than that?Scott Davison: Univar Personal Care is much more than just adistributor; our aim is to add value to our customers’ business.We offer a broad range of products from major principals fromspecialities through to fundamental ingredients. We have a ded-icated sales force supported by a UK and European laboratorycapable of finding innovative formulations to meet any brief.Our technical and marketing teams can offer an insight intotrends and predictions, as well as recommending the rightmaterial. Finally, we deliver our specialities from a dedicatedpersonal care warehouse and our other fundamental ingredi-ents from a network of nine regional warehouses.

Brian Nevin: Surfachem’s role as a distributor has changedin recent years as our focus has moved more towards speciali-ty ingredients. The relationship we have with our principals is alot closer and the approach we take with our customers is moretechnical. We have invested a lot more in technical people inrecent years. We are working more and more with customersat R&D level, with a dedicated technical team on the road inaddition to our existing sales force. This change has meant get-ting much closer to our principals, with whom we adopt a long-

term partnership approach. Regular training is necessary tokeep us up to speed with the new products coming through.The service we provide to customers is paramount and this hasalways been the case for Surfachem.

Gillian Berry: More importantly, we work very hard toensure that it is our principals and customers who regard S.Black as more than just a distributor. We provide complete serv-ices that include technical support, market intelligence andtrend information, next-day sample delivery and supply chainefficiency, forming the basis of long-lasting relationships. A ded-icated European distribution network operation is supported byfully integrated business management systems. Local stock-holding and efficiencies mean we can offer shorter lead timesand rapid responses to requests. Technical support is coupledwith business creation opportunities via marketing trends andconcept ideas, along with formulation examples from our in-house applications laboratories. Our cosmetic scientists candevelop and give advice on all product types, including skincare, hair care, toiletries and colour cosmetics. Furthermore weare very active with REACH and are now able to use theresources of the Azelis Group.

Natalia McDonagh: Cornelius is more than simply a dis-tributor. In addition to sourcing and handling products, we areparticularly strong in product innovation and marketing andhave embraced the idea of using IT advances to make our cus-tomers’ lives easier. We have a sales team of industry experts,who are able to offer extensive advise and support to our cus-tomers, while our group technical centre offers such other ben-efits as new product concepts, bespoke raw material trials forindividual customers, legislative advice, industry trends reportsand more as part of the Cornelius service offer, as well as giv-ing the customers opportunity to outsource their R&D to us.

What value-added services do you offer to yourprincipals in terms of cosmetic science &technology or commercial support and can yougive details from specific projects that you havebeen involved in over the last couple of years?Scott Davison: Our UK and European labs have the capacityto assist customers to meet briefs and create innovative marketformulations. Confidentiality means that we cannot give details,but, working with both consultants and manufacturers, wehave managed to provide top brands with products that meetinternal requirements like cost and ‘free froms’ but also meetconsumer specifications for lasting feel and effectiveness.Working with our key principals, we have also tailor-made test-ing methods to help our customers continue with their legacyof innovation.

Brian Nevin: As previously mentioned, we work very close-ly with our principals. We are first and foremost their eyes andears on the small to medium-sized customers. A lot of infor-mation is passed back in terms of technical trends and particu-lar customer requirements. With the people we now have inplace, we are also able to give an honest formulator’s view toour principals, which we hope can ultimately improve the prod-ucts we promote and the back-up material that goes with them.I can remember a recent example where a key customer came

Davison - Consolidationprocess will continue

McDonagh - Comprehensivetechnical support

Formulate.qxp 7/10/08 12:16




with a specific remit for a hair care product, for which we hadno slot-in product that would do the job. Joint discussion withthe principal yielded a solution, a product not promoted intohair care before but it did the job and performed very well. Thisnow finds itself in a commercial product.

Gillian Berry: Our applications laboratories in the UK andGermany have full stability testing, development and evaluationcapabilities. A team of development scientists have knowledgeof the latest ingredients and their use in new applications.Technical experts can offer assistance at any stage of productdevelopment, including help with formulations and regulatoryadvice. Fully searchable on-line product and formulation data-bases can inspire business creation via new product conceptsand ideas. This service has proved to be highly valuable tomany customers’ development teams. On the commercial front,technical sales managers experienced in the personal careindustry work with customers to deliver sound commercial solu-tions. Our product range allows the opportunity for one-stop-shopping, thereby linking innovation and efficiency with tai-lored competitive packages. Supporting our sales manager, wehave an internal team of experienced customer sales advisorswho offer rapid responses to customer requests.

Natalia McDonagh: Our group technical centre offerscomprehensive technical support and innovation services andhas assisted customers in developing various products. Thisranges from assisting with specific briefs, such as a moisturisingskincare product for a multinational brand owner, to proactive-ly developing innovative formulations - a novel hair colour for-mulation developed by us was approved by a customer inSeptember. Furthermore, technical staff from our customers,including many from blue chips, have taken advantage of theopportunity to spend time in the Cornelius lab.

In the case of large firms with their own sales forceand/or manufacturing in the UK, what is the roleof companies like yours?Scott Davison: Even the largest firms would struggle to contactall customers within the UK personal care market. With a dedi-cated sales team, we can have regular face-to-face contact bothwith buyers and new product development people alike. Ourfield-based account managers are supported by a team of inter-nal account managers assigned to look after customers’ day-to-day requirements. Univar also has a team of technical and prod-uct specialists to give advice on trends and technical support.

Brian Nevin: Most large chemical firms have recognisedthat their core competence is not selling small packs of productto small to medium-sized customers. They also recognise thevalue in selling a package of products, the so called ‘one-stopshop’ approach. As a distributor our core competence is todeliver a package of value-added products to customers in apack type that suits them. We have also invested in the resourceto help customers to develop products. A large chemicals com-pany simply would not be commercially able to put a sales forcein place that would allow it to sell effectively to the full spectrumof customers Surfachem deals with.

Gillian Berry: We specialise in bringing to the UK cus-tomers’ products from around the world that they would nor-mally not have rapid access to, coupled with technical support,full visibility of the supply chain and comprehensive documen-tation and advice on legislation provision. The added valueproposition previously mentioned is key to the service that weprovide. We do not just move product from A to B, we see our-selves as solution providers. S. Black also represents UK-basedprincipals and delivers the same benefits to customers regard-less of location.

Natalia McDonagh: We offer an intimate knowledge of thecustomer base and the flexiblility to deal with customers of allsizes, both of which are capabilities that our large principals findvaluable.

How do you see the role of companies like yoursevolving over the next few years? Will there be acontinuing role for independents or will they tendto be absorbed by large players?Scott Davison: The personal care market faces some tougheconomic challenges as consumer spending is forecast to slowmarkedly. This, combined with large increases in raw materialprices, will see all distributors come under pressure. Being partof a larger company, Univar Personal Care is well placed toweather this storm. Consolidation and acquisition will continueto be a feature of the market and, being part of Univar’sEuropean personal care business, we are able to offer cus-tomers and suppliers a pan-European service. In addition, a keyrole of distributors is to manage regulatory and environmentalissues. This is again a costly process - we have a dedicated teamable to provide advice from the completion of questionnaires toconducting site audits. Finally, as suppliers continue to moveEast, we have people with the necessary training and prepara-tion for REACH.

Brian Nevin: I do see Surfachem continuing to evolve, wewill have to! We will continue to take a technical approach toour business and we will build on our range of products toreflect the changes and hopefully stay ahead of our target mar-kets. There will always be a role for distributors. Simply put, weadd value and this will continue. As for independents, there hasbeen consolidation within our industry but the role of the inde-pendent distributor is still important. Smaller, independent dis-tributors offer a more intimate relationship to customers. We arerelatively free of bureaucracy, can turn thing around quicklyand offer more focus and expertise within our target markets.

Gillian Berry: S. Black became part of the Azelis Group inOctober 2007. For S. Black, this has resulted in a more robustEuropean presence and, for Azelis, a stronger representationand greatly increased technical knowledge of the personal care,healthcare and food sectors. S. Black has the means andresources to grow locally and retain our flexibility, responsive-ness and emphasis on local customer and principal focus, butbeing part of a larger organisation means that we can takeadvantage of the synergies available, as well as having access tocentralised IT, SHEQ, REACH and logistical capabilities.

Natalia McDonagh: Whilst consolidation is inevitable tosome extent, I believe that the strengths of the independents,

S. Black’s laboratory in Hertford, UK





who can offer flexibility and a personal approach, will always bein demand by the customers. Furthermore, independents areoften owned by people who are personally committed to suchideals and who feel that independent distributors are a corner-stone of the personal care industry.

What are the key factors driving the personalmarket at the moment in your opinion?Scott Davison: Price is the dominant factor driving the per-sonal care market at present. Raw material increases have beenon an unprecedented scale, following a long period of relativestability and all players in the personal care market will need toadjust. Retail spend on personal care products in the UK willdrop to below 1%, forcing manufacturers to diversify productsand markets. The demand for naturals and botanicals continuesto be a major trend and an ageing population will see growthin nourishing and anti-ageing products.

Brian Nevin: Natural or naturally derived products, anti-ageing products and REACH

Gillian Berry: REACH. S. Black intends to pre-register allsubstances with which it is involved. Azelis has a very activeREACH unit and offers an Only Representative service to non-EU suppliers. The impact of REACH cannot be underestimatedand will present many issues that will need resolving in thefuture as the SIEFs are formed and registration takes place. SBlack will be working with all our suppliers & customers toensure that all parties are kept fully informed of any issuesresulting from this. Another key factor is the one towards natu-ral and organic products. Datamonitor forecasts that the UKmarket for organic personal care products will increase fromjust over €11 million in 2007 to over €15 million by 2011.Traditionally a niche category, this organic personal care trendis part of a larger movement in the UK towards organic andmore natural ingredients generally. These products are becom-ing more mainstream. A potential barrier to the expansion ofthis sector is the lack of legislation and definition of what is nat-ural and organic throughout Europe.

Natalia McDonagh: In no particular order, the increasingtrend towards natural/green products, textures and improvedclaims.

What new will you be launching or showcasing inTelford this yearScott Davison: New products include SatinFX delivery sys-tems, which are a cost-effective, easy to use encapsulationand delivery system for hydrophobic and hydrophilic actives.It enables formulators to encapsulate sensitive or ‘impossible’combinations of actives and fragrances into a formulationand even reduce their potential skin irritation. Another isLuviquat Sensation, a high performance, silicon-free condi-tioning polymer for rinse-off products that provides soft andnatural hair feel, superior volume control, excellent comba-bility and improved stylability. We are also launching our newpersonal care brochures designed to make it easier for cus-tomers to find the right ingredient for their application,whether it is haircare, skincare, suncare, decorative cosmetics,oral or babycare.

Brian Nevin: We continue to grow our natural productoffering and look forward to promoting these at SCSFormulate this year. We now have a range of SchercemolEsters from Lubrizol Advanced Materials with Ecocert approval,a really nice range of Ecocert-approved products from Evonik,an ever growing range of natural surfactants. One of two newnatural preservatives is still to be confirmed but we are launch-ing GranLux AOX, a spruce knot extract from Granula whichhas anti-microbial and anti-oxidant properties.

Gillian Berry: We will be showcasing the latest ingredientsand formulations from our application laboratory that meettoday’s and tomorrow’s market trends across all aspects of per-sonal care. New delivery systems, for skincare as well as naturaland organic ingredients, will be complemented by hair condi-tioners and fixatives, skin care actives with proven efficacy data,effective sun protection and moisturisers. Analysis of new prod-uct introductions over the last few months has identified the topclaims that manufacturers are making. We will help visitors toour stand to achieve these claims in new ways. New develop-ments in preservation systems as well as hair growth controland products designed specifically for male toiletries will alsofeature. New pearlescent and treated pigments with stunningvisual effects, mild surfactants and soothing butters will assist inthe development of effective personal care products.

Natalia McDonagh: In addition to new products fromour existing principals, this will be the first exhibition at whichwe will be showcasing Jeen International, with its range ofinnovative silicones, and Power Paper, which is offering newand exciting battery-powered skincare patches.

Univar Europe Scott Davison Marketing Manager International HouseZenith, Paycocke RoadBasildon SS14 3DWUKTel: +44 1274 470502E-mail: [email protected] Website: www.univareurope.com

SurfachemBrian NevinMarketing Manager 100 Wellington StreetLeedsLS1 4LTUKTel: +44 113 394 2000E-mail: [email protected]: www.surfachem.com

S. Black Ltd.Gillian BerryGroup Marketing ManagerFoxholes Business Park John Tate Road HertfordSG13 7YH UKTel: +44 1993 825555E-mail: [email protected]: www.sblack.com

CorneliusNatalia McDonaghMarketing ConsultantCornelius HouseWoodsideBishops StortfordCM 23 5RGUKTel: +44 1279 714319E-mail: [email protected] Website: www.univareurope.com

For more information, please contact:

Formulate is the key UK event in cosmetic technology


www.chemspeceurope.com/pharmaspeceurope

200917 – 18 JUNE 2009HALL 1, GRAN VIA EXHIBITION CENTER

BARCELONA, SPAIN

Contact the sales team

Christine Atkinson

Tel: +44 (0) 1737 855 461

[email protected]

Pharmaspec Europe is a dedicated area within Chemspec Europe

Grouping specialised suppliers of fine chemicals and chemistry services to the pharmaceutical industry in an easily identified zone

Attracting a continuous stream of attendees from major players tosmall companies operating within the pharmaceutical market.

In association with:

A feature zone within:

Organised byOfficial media partnerIn association with

Project1 7/10/08 12:29 Page 1




Chirality - a cosmeticchemistry concern?Some claim that ‘chirally pure’ cosmetic products are more effective. Dr Cynthia Challenerinvestigates.

An internet search on chirality these days canprovide some surprising results. Witness, forexample, the websites for several cosmetic

companies located around the world and offeringspeciality product lines based on chiral ingredients.These often make strong statements about theimportance of incorporating chirally ‘correct’ com-pounds into personal care formulations.

“Chirally corrected molecules produce only thepositive effects of each ingredient, dramaticallyreducing the possibility of an allergic or adversereaction,” Cosmedix claims. Signs of prematureageing will be noticeable if “harmful molecules” areleft intact in a product. With its chirally corrected,natural ingredients, users will find that their skin“absorbs the soothing, calming effects of nourish-ment as nature intended.”

“The latest technology of the new millennium -chiral technology” serves as the basis for ZedLaboratories’ Skingenious line of cosmetic products.Using chirally correct ingredients has enabled thecompany to produce “ingenious skin strategies thatdeliver results never before possible,” it claims.

The Skingenious website does, at least, providemore technical information than most. “When askin product’s ingredients are chirally correct, theingredients have the ability to link up properly withthe skin’s receptors and, with that perfect link-up ofingredient to receptor, the product can deliver themost effective results possible with the fewest pos-sible adverse reactions,” the site says.

Sircuit Cosmeceuticals products are “skin care atthe molecular level” according to manufacturerUvasun. “Only chirally correct ingredients canrestore chiral purity and alignment on a molecularlevel, and therefore, on a cellular level,” it states.

The company uses “body friendly” chiral tech-nology and incorporates only ingredient mole-cules with the “right shape,” resulting in “super-charged” formulae. These, it says, “have a higherconcentration of the particular ingredient’s bene-fits, which result in a stronger, more potent, supe-rior product” and also reduce the change for anadverse reaction.

Chirally Correct Skin Care products fromFranché, meanwhile, are said to contain chirally cor-rect ingredients that “are purified to their most nat-ural potent form” and “link up perfectly to the skin’sreceptors to deliver results not possible before.”

Finally, Cosmeceutical International offers its Kyraline of skin, hair and body treatments, which arebased on the use of “optically corrected organiccompounds” and as such “are true cosmeceuticals -pharmacologically active products that blur the linebetween cosmetics and pharmaceuticals”.

The use of chiral resolution techniques enablesthe company to discard “the dangerous rogue side”of optically active substances, it claims. Only chiral-ly correct ingredients possess “the right opticalactivity so as to be recognised and ‘fit’ the chemistryof the human body,” thereby enabling them to “dothe job nature designed them to do.”

Considering the claimsThe general themes running through all of thesecompany websites are that chiral technology is apurification method, that chirally ‘pure’ or ‘correct’compounds are natural, unwanted isomers areharmful and that chirality matters for all personalcare products, from shampoos to lotions.

Chiral technology, obviously, is far more than apurification method. The numerous chemical andbiological synthetic techniques and kinetic resolu-tion methods developed in recent decades specifi-cally for the preparation of isomerically pure chiralcompounds speak to that point.

Many chiral compounds do occur in nature,often in only one form. Vitamin E is a good exam-ple. Natural vitamin E exists as one isomer, where-as the synthetic product is a mixture of eight differ-ent stereoisomers. Studies have shown that the nat-

OHCH3

O

O

OH

OH

H OAc

CH3

CH3H3C

CH2H3C

OH

OH

O

OH3C

H3C

HO

CH3 CH3 COOH

H3C

H

H

H CH3

CH3

CH3H3C

HO

CH3 CH3 COOH

H3C

H

H

H CH3

CH3H3C

CH3H3C

1 2

3 4

O

HNOH

OH

Ceramide 2 [NS]

O

HNOH

OH

Ceramide 3 [NP]OH

Figure 1 - Chirally pure products from Sabinsa

Figure 2 - Ceramide 2 & 3

Chiral.qxp 7/10/08 12:17




ural product is approximately twice as effective assynthetic vitamin E, though the latter is muchcheaper to produce.

However, being a chiral compound does notautomatically make it natural. In fact, mixtures ofvitamin E that contain mostly the synthetic productbut also some natural product can still be callednatural. In addition, a desired enantiomer, initiallyisolated from a plant, may need to be producedsynthetically in order to obtain commercial quanti-ties cost-effectively.

Whilst some undesired isomers do have negativecharacteristics, in many cases the unwanted enan-tiomer is simply not active. There are also exampleswhere both isomers are equally effective.

Ascorbic acid (vitamin C) is one case where thenon-natural isomer is indeed harmful. L-ascorbicacid is an effective antioxidant and also stimulatescollagen synthesis, making it a popular ingredient.The D-isomer, however, often causes dryness, itch-ing and other skin damage. Isolating the pure L iso-mer is difficult, though, and therefore more costly,so most formulations contain the racemic mixture,despite the negative properties of the D-compound.

That leads to the last point. Are enantiomericallypure ingredients really effective in personal careproducts? Does it matter if your shampoo or sun-screen has only one isomer of certain ingredients?

It does not seem likely that chirality would mat-ter for many types of cosmetic products. Shampoosand soaps, for instance, do not interact with biolog-ical systems, so having pure enantiomers of ingre-dients in these products is unnecessary. Sunscreensabsorb UV light, a function independent of stereo-chemistry. Here, too, chirality does not affect theperformance of the product.

For certain skin treatments, however, there is afavourable argument for including isomericallypure active ingredients. Vitamins C and E are goodexamples here as well.

Chemists weigh inSeveral of the cosmetics companies’ websites discussthe idea that the correct enantiomer of a chiral mol-ecule is necessary for interacting with biological sys-tems in the body. These assertions are indeed true.

The key is that the active ingredient must needto react in some way. For products like shampoosthat do not function in this manner, chirality is irrel-

evant. Many of the newer skin treatments on themarket today, however, are designed to affect bio-logical systems.

“Products aimed at causing pigmentation, depig-mentation or cellulite reduction, and those consid-ered as anti-ageing or anti-wrinkle formulations, doinfluence biological process via specific interac-tions,” notes Dr Mike Farwick, head of R&D foractive ingredients at the Consumer Specialitiesbusiness of Evonik Goldschmidt.

The active ingredients in these types of skinpreparations are often peptides or amino acids thatare interacting with enzymes, carbohydrates orDNA.

“Whenever a chiral molecule interacts with anenzyme, one can anticipate differences in thedegree of interaction between them. Hence therecould be a difference in their efficacy,” says DrKalyanam Nagabhushanam, head of R&D atSabinsa.

Substances that claim to be enzyme inhibitors orpotentiators would fall in this category. Someenzymes within the skin that have been targetedinclude tyrosinase, collagenase, elastase andornithine decarboxylase.

Nagabhushanam is quick to point out, though,that there are several enzyme inhibitors that areeither achiral or even if chiral, exhibit equivalentpotency regardless of stereochemistry. For example,Sabinsa’s tetrahydrocumminoid CG is an achiralinhibitor of tyrosinase.

“It is not always necessary to have isomericallypure active ingredients, and formulators shouldonly invest in more expensive enantiomericallypure ingredients if they are truly necessary,” hesays.

In some cases, such as with many ingredientsisolated from natural products, only one stereoiso-mer is present in the plant and therefore the prod-ucts are only produced in chirally pure form.Sabinsa has many such products, includingForskolin, the active ingredient in Forslean CG(Figure 1, 1), Glabridin (2), ursolic acid (3), oleano-lic acid (4), Boswellin CG and Centellin CG.

Because these products naturally occur as oneisomer, only that isomer is tested for efficacy andtoxicity. “If the molecule is highly complex, onlyrarely will the other isomer by synthesised and eval-uated,” Nagabhushanam notes. In the case of pep-

tide-related products, he adds that it is rare fordevelopers to synthesise and evaluate the non-nat-ural amino acid based products.

Ceramides: Chiral chemistry countsEvonik Goldschmidt has investigated ingredientsthat can address changes in the lipid composition ofthe stratum corneum, or outermost layer of theskin. The company has developed a range of stere-ospecific phytosphingosine-based ceramides, whichare the major epidermal lipid component and arekey to maintaining epidermal integrity.

To confirm the importance of the stereochem-istry, studies were conducted with enantiomericallypure Ceramide 3 and a racemic mixture ofCeramide 2 (Figure 2). In two separate samples, thenatural barrier ceramides were purified, spiked withthe two ceramide versions and reconstituted.

The samples were then evaluated with X-ray dif-fraction. The Ceramide 3 was completely integratedinto the mixture of human lipids, while the racemicmixture of Ceramide 2 caused disruption in thelipid matrix.

Further in vitro studies showed that cells incubat-ed with the racemic Ceramide 2 underwent senes-cence. “We believe these results directly correlate tothe incompatibility of the non-skin-identicalceramides with the subcellular structures,” Farwickexplains.

In clinical studies, Evonik found that Ceramide 3demonstrated efficacy for the treatment of dry skin,causing significant skin hydration and firming. Italso was shown to restore the skin barrier, provid-ing skin smoothing and a reduction of fine lines,indicating that the product is biocompatible withthe human skin lipids.

The company has synthesised a series of fiveskin-identical (stereospecifically correct) ceramidesbased on sphingosine and phytosphingosine. Theseingredients were used to prepare an optimised for-mulation containing behenic acid (a fatty acid) andnon-animal cholesterol, with the molecular ratiosdesigned to mimic the lipid structure within thehuman stratum corneum. Tests have shown that themixture provides skin protection and also improvesthe preventive and regenerative properties ofmature skin.

The ceramides are produced using a yeast fer-mentation process followed by deacetylation toobtain the free sphingoid base (Figure 3). The baseis then reacted with a fatty acid to produce theceramides, which possess the identical stereochem-ical configuration as those naturally present in theskin.

According to Farwick, Evonik is continuing topursue the development of enantiomerically pureactive ingredients for cosmetic products. Theseingredients in general are for skin care and hairapplications.

Other factorsThe difference in the activity of stereoisomers inbiological processes within the body is not the onlycharacteristic that may determine the need for useof a single isomer active ingredient. Factors com-pletely unrelated to efficacy may also be important.

Fermentation

Recovery(TAPS)

Chemicalcoupling

Phytosphingosine

Phytosphingosine-basedceramides

Figure 3 - Production of phytosphingosine-based ceramides

Chiral.qxp 7/10/08 12:17




Toxicity to the skin - the ability to cause irritation orallergic reactions - as mentioned by many of thecosmetic companies - is indeed a relevant issue.

“Any difference in toxicity between the isomer onapplication to the skin may point out to a preferredenantiomer, even if chirality does not contribute tothe functionality of the compound in question,”asserts Nagabhushanam. Thus for sunscreens withactive ingredients containing chiral centres, forexample, one isomer may be preferred over theother because it does not act as an irritant.

Environmental fate issues should also be consid-ered. Personal care products can be used in largequantities, and significant amounts of these materi-als can find their way into the environment.

“Even when the efficacy and toxicity profiles arethe same for both optical antipodes, it may still bepossible that one isomer is more toxic to the envi-ronment than the other,” Nagabhushanam says.Another possibility is that one isomer may degrademore quickly to harmless products than the other.

Dermatologist viewWith the development of more and more cosmeceu-ticals, formulators of cosmetic products are narrowingthe gap between pharmaceutical products and cos-metics. Consumers are consequently turning to der-matologists for recommendations on product efficacy.Given this trend, it is worth finding out how a skinspecialist views the increasing claims by cosmeticcompanies regarding ‘chirally correct’ ingredients.

“I feel that many companies place a lot of unnec-essary emphasis on the chirality of their productsfor marketing purposes,” states dermatologist andMohs skin cancer surgeon Dr Jennifer Linder, whois also chief scientific officer at PCA Skin.

“Although there is scientific validity for the use ofchirally correct ingredients, this is not the only thingto base a truly beneficial product line upon. The useof an ingredient that shows no evidence of topicalbenefit will often still have no topical benefit regard-less of its chirality.”

“A well-formulated topical product should con-tain the most effective ingredients available; insome cases, this may include the use of chirally cor-rect ingredients, but it is also imperative that prop-er molecule stabilisation, effective delivery systemsand ingredients with scientific substantiation beused.”

The final analysisThe chirality of active ingredients in personal careproducts can play a role if the ingredients interactwith biological systems, which is most oftenobserved for skin treatment formulations. Variationsin the toxicity and environmental fate of differentisomers may also be important in determiningwhether or not optically pure ingredients are appro-priate. For many products, though, where cosmeticscompanies would like consumers to believe that‘chirally correct’ means more effective, it often sim-ply means ‘more expensive’.

Evonik Goldschmidt Dr Mike FarwickHead of R&D Active Ingredients - ConsumerSpecialtiesGoldschmidtstr. 100D-45127 EssenGermanyTel: +49 201 173-2351E-mail: [email protected]

SabinsaDr Kalyanam NagabhushanamPresident, R&D70 Ethel Road West, Unit 6PiscatawayNJ 08854USATel: +1 732-777-1111E-mail: [email protected]

PCA SkinDr Jennifer LinderChief Scientific Officer8501 N. Scottsdale Road, Suite 150ScottsdaleAZ 85253USATel: +1 480.946.7221E-mail: [email protected]

For more information, please contact:

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A novel low-temperatureextraction of botanicalsDr Charles Scanio and Patrick McFadden of Naturel Extracts describe a new extraction process

Currently there are four fundamentally differentbut commercially viable methods to obtainactive ingredients from naturally occurring

botanical substances. The method of choice dependsto a large degree upon the material to be extracted.All have their pros and cons.

Steam distillation is the most common method inuse today. This process is cost-effective and relativelysimple both to use and to scale up. Extractions aregenerally fast, with good yields and low start-up costs.It is used to extract flavours, fragrances, dyes, pharma-ceuticals, nutraceuticals and cosmeceuticals.

However, steam distillation does have disadvan-tages, such as the extensive thermal degradation andloss of volatile components caused by the high heatused. This reduces the quality of the extract, makingthe process unacceptable for sensitive botanicals oressential oils that are difficult to extract. Moreover, thehigh energy costs needed to generate steam make theoverall process operating costs high.

Expression is used primarily in the food industry toobtain oils from nuts, seeds, olives, grapes, etc. Highpressure is applied to the material to generate the oils.No heat is required, scalability is not an issue and theprocess affords good quality extracts in good yieldswith relatively low start-up costs.

However, expression is not at all useful for extract-ing most leafy, dried botanicals and is, in fact, a some-what antiquated extraction technique. In addition,start-up costs can be relatively high, depending on thescale of the operation.

Supercritical CO2 is a fairly new technology that isused to extract flavours, fragrances, dyes, pharmaceu-ticals, nutraceuticals and cosmeceuticals. It uses CO2

under pressure high enough that the gas is above itscritical point, which gives CO2 excellent solvent prop-erties. The extractant is non-toxic, odourless, relativelyinert and inexpensive. Scalability is not an issue andCO2 removal is very easy.

The downside is that considerable technical skillsare required to operate the equipment. In some cases,moreover, the high pressure can damage sensitiveand delicate botanical extracts and residual moisture inplants often generates carbonic acid, turning extractedoils rancid. Finally, start-up costs are very high.

Organic solvent extraction is one of the mostcommon botanical extraction methods used today,typically using hexane, methylene chloride, fat andvarious alcohols to extract flavours, fragrances, dyes,pharmaceuticals, nutraceuticals, and cosmeceuticals.This method is relatively cost-effective, yields are gen-erally good and the extracts are of good quality.

The main problem is that extractions are generallyconducted at reflux, resulting in thermal degradationof the extract. If ethanol is not used, potentially toxicsolvent residues contaminate the extract.

New processFollowing several years of R&D, testing, scale-up andvalidation, Naturel Extracts has developed a novel, lowtemperature, solvent extraction process that obviatesmany of the disadvantages of current methodologies.1

Earlier work describes numerous botanical solventextraction methods.2-3

Our initial experiments focused on the use ofethanol because of its high solvent power, non-toxici-ty and low boiling point under reduced pressure. Weused both 190 and 200 proof ethanol, typically dena-tured for cosmeceuticals and undenatured fornutraceuticals.

It soon became evident, however, that ethanol, likevirtually all the other organic solvents we examined,can extract numerous organic materials from botani-cal products. Some of these are undesirable in the finalextracted product. As our experience with the natureof the undesirable impurities increased, we were ableto develop an efficient, four-step extraction process:

1. A 3-5 hour low-temperature ethanol extraction ofa dried, milled botanical

2. Addition of a base or activating agent to theethanolic extract, increasing the pH and thus pre-cipitating impurities, which are removed from theextract solution by filtration or centrifugation

3. Addition of an acid de-activator to neutralise thebase, allowing the removal of additional impuritiesand salts

4. Low-temperature vacuum distillation of theethanol, affording a highly concentrated, alcohol-free residue, containing essentially all of the origi-nal active components and oleoresins

Key advantagesThis process has numerous advantages, starting withreduced thermal degradation. All operations are car-ried out at low temperature eliminating thermal degra-dation and/or the volatilisation of the active ingredientsin the botanicals.

Whilst it is necessary to use ethanol as the extract-ing solvent removing all traces of it can be difficult.However, this is not a major problem, since many cos-metics and flavouring agents are alcoholic solutions.

The quality and potency of the oleoresins obtainedby the process are exceptionally high. This has beenconfirmed by high oxygen radical absorbance capaci-ty values found in certain extracts. Likewise, the yieldof principal active components, essentially devoid ofimpurities, is high.

The process depends somewhat upon the plantspecies, its physical state (how finely milled it is) andhow dry it is. Nonetheless, it can be readily scaled upafter a single, small-scale laboratory experiment. It hasbeen demonstrated and validated on a wide variety of

botanicals, including lavender, cinnamon, vanillabeans, crowberry, wormwood (above), fireweed,Alaskan ginseng and walnut mash.

Start-up costs are low because the process does notrequire highly specialised equipment and can be con-ducted in virtually any multi-purpose batch organicchemicals facility equipped with glass lined, stainlesssteel vessels and centrifuges or alternative filtrationequipment. A relatively high level of technical skills,however, is required to run the process.

The extraction scales up easily, as evidenced by thefact that we have gone directly from laboratory scaleextractions in a 2 litre flask to plant-scale (400-1,500litre reactors) with no problems. The entire process canbe completed, in the plant, in fewer than two shifts.

Finally, the process is environmentally friendly. Theextractions and distillations are conducted in essential-ly closed systems. The ethanol is recycled and theimpurities that are removed from the extract (typicallylignin) are biodegradable. In some cases, this by-prod-uct can be used in cosmeceuticals. The residue fromthe initial extraction can be composted. Alternatively, itcan be dried and subsequently extruded into woodpellets.

References:1. USP 6,962,725 & EP(UK) 1,397,186, to Naturel ExtractsInc..2. M. Heinrich, J. Barnes, S. Gibbons & E.M. Williamson,Fundamentals of Pharmacognosy & Phytotherapy, ElsevierHealth Sciences, 2004, 143ff and references cited therein.3. www.essentialoils.co.za/solvent-extraction.htm

For more information, please contact:Dr Charles J.V. ScanioChief Scientific OfficerNaturel Extracts Inc.300 High StreetP.O. Box 246Winchendon, MA 01475USATel: +1 978-297-3333E-mail: [email protected]

Natural.qxp 7/10/08 12:17


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Dr Yasushi Matsumura of Asahi Glass introduces new difluorination techniques for APIs and intermediates

Halo-organics

It is well known that the introduction of fluorineatoms to biologically active substances maylead to improvements in their pharmacological

properties and therapeutic efficacy.1 The advanta-geous pharmacological effects of fluorinated mol-ecules are mainly derived from the physicochemi-cal characteristics of fluorine: its relatively smallsize, high electronegativity and enhancedlipophilicity and the high energy of the C-F bond.

Many fluorinated candidate drugs have beenreported since the first successful development offluorocorticoids in 1950s. This has gone hand inhand with rapid progress in synthetic methods offluorine chemistry.

The vast majority of these compounds containeither a single fluorine atom or a trifluoromethylgroup attached to an aryl or heteroaryl ring. A rel-atively small number contain fluorine atomsattached to aliphatic carbon atoms, with a sub-group containing geminal difluorides (CF2).2

Largely because of the difficulty of synthesisingthem on a large scale, gem-difluorinated com-pounds have rarely entered production, but theyhave recently attracted considerable attention dueto their excellent characteristic profiles. This articleintroduces recently marketed gem-difluorinateddrugs and the development of new difluorinationtechnologies by Asahi Glass applicable to APIsand their intermediates.

Novel gem-difluorinated drugs Novel compounds with geminal difluoride unitshave been approved as new drugs with important

pharmacological profiles every year of late. Thesecompounds are designed to meet the particularneeds by taking advantage of the unique natureof fluorine.

For example, the gem-difluoromethylenereplacement of a CHOH-linkage has been used toachieve significant effects in carbohydrate andprostaglandin systems. The cyctosine analogueGemicitabine (Figure 1, 1) is widely used to treatnon-small cell lung cancer, pancreatic cancer,bladder cancer and breast cancer. The compoundinhibits DNA replication and DNA repair by‘mimic effect’ as an anti-metabolite.

A new anti-glaucoma drug, Tafluprost (2), has aunique CF2 group in place of a CHOH group ona prostaglandin skeleton. This exerts highly potentand selective FP receptor agonistic activity. Itsdesign has made a great impact because thehydroxy group of prostaglandins had beenthought to be essential to pharmacological activi-ty. The compound exerts a potent and stableintraocular pressure-reducing effect and alsoincreases the effect of blood flow in the head ofthe optic nerve.

The high electronegativity of fluorine ensuresthat the electronic nature of the CF2 group is adominant characteristic. α,α-Difluorination ofketones imparts increased electrophilicity to thecarbonyl and a consequent propensity for the for-mation of stable hydrates and hemiacetals.

Lubiprostone (3) is a novel 15-keto-16,16-difluo-ro-prostaglandin E2 derivative that is mainly


New perspectives on difluorination

N

N

NH2

OO

OH F

HOF

Gemicitabine(Eli Lilly, 1995)

anti-cancer

NHO

FF

NN

NN

CH3H3C

H3C

Maraviroc(Pfizer, 2007)

anti-HIV

CO2H

O

O

HOF F

Lubiprostone(Sucampo, 2006)

constipation

O

FFHO

HOCO2Pri

Tafluprost(Santen, Asahi Glass, 2008)

anti-glaucoma

1 2

3 4

Figure 1 - Marketed gem-difluorinated drugs

R1R2

O

R1R2

O

FF

MnBr2(PhSO2)2NFKN(SiMe3)2

Substrate Difluorinated product Yield (%)

OMe

O

OMe

O

FF

93

O O

F

F80

TBSO

O

O

OTBS TBSO

O

O

OTBS

F

F 67

Table 1 - α,α-Difluorination with NFSi-KN(SiMe3)2-MnBr2

Asahi_Glass.qxp 7/10/08 12:17

formed as a bicyclic hemiacetal. It exists as stablecrystals or a crystalline powder because of the elec-tron-withdrawing effect of the fluorine atoms. Thecompound is used in an oral treatment for consti-pation. It has a unique action that activates a local-ly acting chloride channel of the human intestine.

Maraviroc (4) is a potent antagonist of theCCR5 receptor that is used as a treatment for HIV.The structure includes a 4,4-difluorocyclohexylunit with a high antiviral profile; this lacks a block-ing affinity for the HERG ion channel whichrelates to QT prolongation. The 4,4-difluorocyclo-hexyl group probably brings low affinity to the ionchannel, due to the steric demands of the cyclo-hexyl moiety and also the dipole generated by thedifluoro unit.

Difluorination technologiesThe preparation of gem-difluorinated moleculesfalls into two approaches. The first uses variousfluorinated synthons, such as halodifluoroacetates,halodifluoroketones, dibromodifluoromethane, tri-fluoroethanol, trifluoroacetic acid derivatives, triflu-orotrimethylsilane and tetrafluoroethylene, but thecommonest is the Reformatsky reaction of halodi-fluoroacetates and halodifluoroketones.

Although many new and effective reactionshave been developed, applications are limited bythe availability of different fluorinated synthons.The second approach involves gem-difluorination,which is quite a powerful technique, particularlywhen used at a late stage in a synthetic route oncomplex intermediates.

One approach that is rapidly becoming one ofthe most important methods is electrophilic flu-orination.3 In this approach, fluorine acts as anelectrophile rather than as a nucleophile or a rad-ical.

Many fluorinating reagents have been devel-oped over the last 50 years, such as elemental flu-orine, perchloryl fluoride, xenon fluoride, hypoflu-orites and N-fluoro compounds. The latter include1-chloromethyl-4-f luoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate (Selectfluor),N-fluorobenzenesulphonimide (NFSi), N-fluo-ropyridinium salts (Umemoto’s reagent) and oth-ers. Nevertheless, selective electrophilic difluorina-tion remains a difficult task.

Asahi Glass has developed the technique byusing NFSi with potassium bis(trimethylsilyl)amideand manganese bromide. This is one of the mostefficient methods yet reported to convert esters orlactones to the corresponding difluorinated onesselectively in a single step.4 The reaction has beenapplied as a key step in the synthesis of compli-cated molecules, such as prostaglandin intermedi-ates (Table 1).

We have also worked to develop more reactivereagents for electrophilic difluorination. The cyclicDesmarteau reagent showed higher reactivity thanNFSi and Selectfluor for the difluorination of α-


Halo-organics


rination technology

R1 R2

O

R1 R2

FF

O NSF3

R O RCl

ClR Cl R

F

F

PCl5 HF+

Figure 2 - Allylic difluorination & sequential chlorination-difluorination


Halo-organics



ketoester under mild conditions, giving thedesired difluoride in 90% yield (Table 2). By con-trast, Selectfluor gave it in 41% yield, with 52% ofthe corresponding monofluoride. NFSi also result-ed in a mixture of difluoride and monofluoride inlow yield.

Nucleophilic difluorination is another impor-tant method. Diethylaminosulphur trifluoride(DAST) and sulphur tetrafluoride have often beenused for the gem-difluorination of ketones andaldehydes. Surprisingly, though, there is no gen-eral, efficient method for the preparation of allyldifluoride from the corresponding enone. Westudied the reaction and found that the fluorina-tion reaction of enones with morpholinosulphurtrifluoride in chloroform gave geminal difluoridesin high yield (Figure 2).5

Hydrogen fluoride (HF) is the simplest and mostpractical fluoride for nucleophilic fluorination. Thenucleophilic substitution of a hydroxyl group withHF has often appeared in the literature.Nevertheless, it had been only used as a fluoridesource of BrF or IF formed in situ in the reactionsof dithioacetals, hydrazones, oximes andacetylenes to the gem-difluorides.

Asahi Glass recently developed gem-difluorina-tion of ketones via a mixture of the gem-dichlo-ride and vinyl chloride using HF (Figure 2). Themixture of chlorides is easily obtained from theketone by treatment with phosphorous pentachlo-ride. The fluorination reaction proceeded efficient-ly to provide the desired difluoride in high yield.The process is regarded as one of the most prac-tical methods for gem-difluorination in large scale.

Professor S. Hara at Hokkaido University report-ed a new difluorination reaction using iodinepentafluoride (IF5) (Figure 3).6 Starting from thesulphides at the α-position of carbonyl com-pounds, the reactions with IF5 gave the corre-sponding gem-difluorides in high yield. Varioustypes of gem-difluoro ketones, esters, and nitrileswere prepared by this novel methodology. Weplan to study the reactions in detail and extendtheir applicability in industry.

References:1. A. Tressaud & G. Haufe, Fluorine & Health, Elsevier,Amsterdam, 2008; I. Ojima, J.R. McCarthy & J.T.Welch, Biomedical Frontiers of Fluorine Chemistry, ACS,Washington, DC, 1996; T. Hiyama, OrganofluorineCompounds, Chemistry & Applications, Springer, Berlin,2000; K. Uneyama, Organofluorine Chemistry,Blackwell, Oxford, 2006; J-P. Begue & D. Bonnet-Delpon, J. Fluorine Chem., 2006, 127, 992; K.L. Kirk, J.Fluorine Chem., 2006, 127, 10132. M.J. Tozer & T.F. Herpin, Tetrahedron, 1996, 52,8619; J. M. Percy, Chimica Oggi 2004, 183. S.D. Taylor, C.C. Kotoris & G. Hum, Tetrahedron,1999, 55, 124314. T. Nakano, M. Makino, Y. Morizawa & Y. Matsumura,Angew. Chem. In. Ed. 1996, 35, 1019; Y. Matsumura,T. Nakano, N. Mori & Y. Morizawa, Chimia, 2004, 58,1485. Y. Matsumura, N. Mori, T. Nakano, H. Sasakura, T.Matsugi, H. Hara & Y. Morizawa, Tetrahedron Lett.2004, 45,15276. S. Hara et al. Ann. Meeting Chem. Soc. Japan(Tokyo), 2008, 1J4-51

For more information, please contact:Dr Yasushi MatsumuraDirector - Advanced Organic SynthesisLaboratoryAGC Chemicals Asahi Glass Co., Ltd.1150 Hazawa-cho, Kanagawa-ku,Yokohama 221-8755JapanTel: 81-45-374-7744E-mail: [email protected]: http://www.agc.co.jp/

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OEt

O O

OEt

O O

FF

Electrophilicfluorinating agent (2.0 eq.)

rt

Notes: a Determined by 1H and 19F NMR; b 52% monofluoro adducts (keto and enol form) were alsoobtained; c 8% mono-fluoro adducts were also obtained

Table 2 - α,α-Difluorination with cyclic Desmarteau reagent

Fluorinating agent Solvent Time (hours) Conv. (%) Yield (%)a

SO2

N

O2SF

F

FF

F CCIF2CF2CCl2CF2CF2Cl 20 100 90

N+ N+ F

Cl

2BF4–

CH3CN 20 92 41b

(PhSO2)2NF THF 92 28 6c

X

SR

O

R' X

O

R'FF

IF5

X: aryl, OR1, NR2, etc

Figure 3 - Difluorination with IF5



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Halo-organics


Easy-clean or super easy-cleanSteven Block of Dow Corning and Salvatore Re of Daikin Chemicals Europe report on the development of new generations of surface modifiers*

Designing surfaces that stayclean longer or that can becleaned easily has always

been one of the fundamental goalsof surface chemistry research.Organofluorine chemistry and sili-cone chemistry have been widelyused in surface modification systemson a wide variety of substrates,including textiles, leather, stone andpaper.

Research teams from Daikin andDow Corning are working togetherto combine the benefits of fluorineand silicone chemistry in order todevelop new surface modifiers.These are designed to meet thehighest performance standards inapplications where these characteris-tics are valued.

Macro trendsTwo major trends in the world todayare increasing opportunities for stay-clean and easy-to-clean surfaces. Themost obvious trend is the rapidlyincreasing use of electronic deviceswhere human interface is necessaryfor operation. Touch screen phones,

MP3 players and GPS systems aretypical device displays where opticalclarity and ease of cleaning are valu-able features.

This trend will clearly continue inthe coming years with advancedgraphics, where clarity is requiredfor optimum performance. It alsoshows signs of spreading into lessdemanding areas, such as windowsand mirrors. In the coming years, itwill be common for a surface tohave both stay-clean and easy-to-clean performance.

Research is being conducted inacademia and industry and varioustechnical routes have been pro-posed to achieve this. At present,however, a chemical surface modifi-cation is the most realistic method.There are theoretical models underconsideration of how to get the ‘per-fect surface’ but these ideas have yetto be proven practical and durable.

A second trend is simply that, withthe ageing of the baby boomer gen-eration, any feature that reduces timeto clean and improves aesthetics willbe valuable. People look for products

that require little or no maintenanceor cleaning, so as to give them morefree time instead of spending time onmundane chores. This segment of thepopulation is willing to pay for thesefeatures to enhance their lifestyle,such as in kitchen appliances andshower doors.

Surface modifiersVarious stain-proofing agents havepreviously been proposed as solu-tions to the problems related to oil-and water-repellency. These have

included a stain-resistant anti-reflec-tive coating obtained by surfacetreating a substrate with a perfluo-roalkyl group containing compoundand a stain-resistant low-reflectionplastic with a polyfluoroalkyl groupcontaining mono- and disilane com-pounds and halogen, alkyl oralkoxysilane compounds as a surfacemodification coating. A third optionis forming a copolymer of perfluo-roalkyl (meth)acrylate and alkoxysilane group containing monomeron an optical thin film consistingmainly of silicon dioxide.

However, these coatings haveinsufficient stain resistance proper-ties, especially on the most impor-tant stains, such as fingerprints, skinoil, sweat and cosmetics. Obtainingthe desired performance of highwater and oil contact angles and lowsliding angles requires the chemicalmodification of a linear perfluo-ropolyether (PFPE).

Four alkoxysilyl perfluoropoly-ether adducts were synthesised(Figure 1, 1-4). Performance testswere then done to assess their stay-clean and easy-to-clean perform-ance. These silyl modified PFPEswere applied on glass test piecesand evaluated for contact and slid-ing angle for water and n-hexade-cane (Table 1)

The key to high performance herederives from combining the benefitsof the perfluoropolyether tail withthe reactive alkoxy silane. In themost successful applications, thesilane group reacts with the sub-strate preferentially, resulting in acovalent bond between the treat-

F OCH2OCH2CH=CH2

F F

FF

F F F F

n

F OCONHCH2CH=CH2

F F

FF

F F F F

n

F OCH2O(CH2)Si(OMe)3

F F

FF

F F F F

n

F OCONH(CH2)3Si(OMe)3

F F

FF

F F F F

n

FF

FF

FF

FF

1

3

F OCH2O(CH2)SiMe2OSiMe2(CH2)2Si(OMe)2

F F

FF

F F F F

n

F OCONH(CH2)3SiMe2OSiMe2(CH2)2Si(OMe)

F F

FF

F F F F

n

FF

FF

2

4

Cl3SiHCH(OCH3)3

(MeO)3Si(CH2)2SiMe2OSiMe2H

1 2 3 4Contact angle for water (deg) 113.0 110.6 110.9 108.7Contact angle for n-hexadecane (deg) 67.1 64.6 69.9 67.0Sliding angle for water (deg) 3.2 4.7 5.2 8.8Sliding angle for n-hexadecane (deg) 3.1 4.3 3.8 6.0

Figure 1 - Synthesis of alkoxysilyl perfluoropolyether adducts

Table 1 - Measurements of silyl modified perfluoropolyethers

Table 2 - Contact angle hysteresis

Water n-HexadecaneContact angle 114.5 67.9Sliding angle 3.5 4.0Advancing angle 119.7 71.7Receding angle 117.4 67.5Hysteresis 2.3 4.2

Daikin.qxp 7/10/08 12:18

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ment chemical and the surface andthus giving optimum orientation aswell as chemical bonding.

Meanwhile the long, flexible PFPEtails cover the surface in what can beenvisaged as a hair-like structure.These ‘hairs’ will naturally reach anequilibrium condition relative toeach other, resulting in the lowestsurface energy.

Predicting performanceMeasuring easy-to-clean or stay-clean properties is done indirectly bylooking at the contact angle of afluid to the rigid surface in both stat-ic and dynamic states.

Consider a drop of liquid on a flatsurface. If the droplet is highlyattracted to the surface, it will tendto spread out and try to wet the sur-face completely.

In this case, there is a very smallcontact angle and the surface isdefined as being hydrophilic oroleophilic. These surfaces have acontact angle of <30°.

Conversely, a hydrophobic oroleophobic surface cause the liquiddrop to bead up, giving a contactangle of >90°. The higher the con-tact angle, the more the surfacewants to repel the liquid.

Stay-clean surfaces have higherliquid contact angles - the higher theangle, the better the stay-clean per-formance. The contact angle pro-

vides information directly on theinteraction energy between the sur-face and the liquid and therefore onthe surface aesthetics in use.

Since all of the surfaces underconsideration will be subjected tosome type of rubbing or abrasion, acritical aspect of a hydrophobic coat-ing is retaining initial performanceover a long period of time in actualservice. Obtaining a very high initialcontact angle and/or a low slidingangle is much less difficult thanachieving the targeted contact angleafter durability testing.

Measuring the hysteresis of a liquiddrop gives an indirect prediction ofeasy-to-clean performance. Hysteresisis the difference between the advanc-ing and receding contact angle. Thistest is performed by placing a fixedvolume of liquid on a solid surface.

Once this drop is resting on thesurface, the receding angle isobtained when liquid is removedfrom the drop without changing thesurface to liquid contact area. At thepoint in time when the liquid to sur-face interface area changes, thereceding angle is determined.

When the liquid is added to thedrop on a rigid surface, the advanc-ing angle is obtained at the momentjust as the interfacial area increases.The difference between the advanc-ing and receding angle is the con-tact angle hysteresis (Table 2). The

lower the hysteresis, the easier thesurface is to clean.

Think about what this means in areal application. For example, take aglass surface on the front of akitchen oven. When dirt or oil con-taminates the chemically treated sur-face, which is meant to give a nicelook to the kitchen, a low hysteresismeans that the contaminant can bewiped off very easily, without leavinga smudge or haze behind.

Typical applications Surfaces where aesthetics are impor-tant are all candidates for this mate-rial which gives superior hydropho-bic and oleophobic performance.Acute clarity is certainly needed onelectronic displays where theirincreasing detail and smaller size ofrequire the screen to have optimumoptical clarity.

Consider the new generation ofsmart phones, where the display sizeis typically less than 50 cm2 andsome are as small as 25 cm2.

Pictures, web pages and stream-ing video all demand optical clarity.Those viewing movies or playinggames will need and value stay-clean and easy-to-clean surfaces andthese have been proven achievableto the highest level using this newtechnology.

Practical uses in kitchen appli-ances where cooking oils are com-mon make this coating a nice fit ineasy-to-clean surface applications.The use of materials like glass, stain-less steel and brushed aluminiumcomponents are becoming verypopular in residential appliances.

However, these materials showdirt very well and cooking oils andcommon kitchen contaminants arevery difficult to clean. The surface isusually smeared with residue and ittakes multiple cleanings and rinsingsto get clean, adding unwantedcleaning time.

Oleophobic coatings have a lowcoefficient of friction. The coefficientof sliding and static friction for PFPEsilane are 0.67 and 0.66 respective-ly, by comparison with 0.77 in both

cases for C8F17(CH2)2Si(OMe)3.Thus, they have quite good wipabili-ty after only a few cleaning strokesand typical oils can be removed to<0.1% haze in five strokes.

Methods of applicationApplying these surface modificationmaterials is a critical step to gettingthe best possible performance.Studies have been conducted toassess the effect of coating methodon oleophobic and hydrophobic per-formance. The most common meth-ods of application are by dip coatingand chemical vapour deposition(CVD).

There are certainly advantages toboth options from the processingperspective. Using dip coating, it ispossible to coat much larger compo-nents. A dip time of 30 seconds isnecessary when using a very diluteliquid bath of approximately 0.1-0.2wt% in order to wet out fully anddeposit sufficient coating.

The solvent is allowed to evapo-rate, then the component is post-washed in a sonication bath toremove any residual material. Afterthat, the coating itself reacts via con-densation, so the PFPE silane poly-mer is covalently bonded to the tar-get substrate. This condensationreaction is kinetically controlled bythe environmental temperature andhumidity.

Raising the temperature from25ºC to 50ºC at a constant 50% rel-ative humidity reduces the totalreaction time from around eighthours to about one hour. Installing acontrollable cure chamber canimprove productivity if there is a rea-son and economic justification forthis additional process step.

A benefit of CVD is eliminatingthe need to handle liquid chemicals.It also removes the need to dilutethe coating bath accurately, thenevaporate and recover the dilutionsolvent.

With this process, a chamber isevacuated, typically to a pressure of 1x 10-5 torr. The coating material,which has previously been deposited

ean Table 3 - Performance of C6Rf silanes v. C8Rf silanes

96

98

100

102

104

106

108

110

112

114

60

70

80

90

100

110

120

Wat

er c

onta

ct a

ngle

Wat

er c

onta

ct a

ngle

0 1,000 2,000 5,000Rubbing cycles

0 500 1,000 1,500 2,000

UV exposure time (hours)

C8F17(CH2)2Si(OMe)3

PFPE Silane

a

b

Figure 2 - Effect of rubbing to water contact angle (a) & UV light resistance(b) of PFPE silane v. traditional silane

Surface modifier Water contact n-Hexadecane contactangle angle

C8Rf (I) 105.0 63.1C8Rf (II) 111.2 72.9C8Rf (I) 111.8 74.4C8Rf (II) 110.6 73.3C8Rf (III) 105.4 64.3C8Rf (IV) 109.4 71.8

Daikin.qxp 7/10/08 12:18

Halo-organics



on a small carrying pellet, is subjectedto an electrical charge. Once thisoccurs at this low pressure, the chem-ical is vapourised in the chamber andis deposited on the target substrate.This is a very efficient process forsmall parts like eyeglass lenses.

Fluoroalkyl silanesThe super-hydrophobic and super-oleophobic PFPE silanes describedabove are designed for the most dif-ficult and demanding uses, such asfingerprint resistance on touchscreens. However, there are manyless demanding applications wheresimple oil- and water-repellency areneeded. In the past, this market was

served by fluorosilanes containingC8F17 end groups.

Due to changes in the fluoro-chemical world, these materials aredisappearing from the market andreplacements are needed. Daikinand Dow Corning are actively devel-oping products for these areas.Many options are possible and it islikely that several products will even-tually be available, each tailored tospecific applications.

These molecules will have asmaller fluorochemical end groupand some kind of reactive silanechemistry; exactly which dependson the end use. However, they willall have certain basic physio-chemi-cal characteristics.

The resulting treatment will havevery low surface energy - in theregion of 12-15 dynes/cm2, withwater contact angles above 110˚.Just like the super-hydrophobicmaterials, these can be applied in anumber of ways includingCVD/PVD, dipping and sputtering.

As suggested above, these shortchain fluorosilanes tend to be usedfor less demanding mass marketapplications. Often these applications

are described in terms of easy-cleanperformance rather than the ultimatestay-clean performance oftenrequired in super-hydrophobic enduses.

Typical examples range from show-er screens to automotive mirrors andhygienic and sanitary surfaces, such asbathroom ceramics. Other applica-tions rely on oil- and water-repellencyin such diverse areas as oil barrier lay-ers in electronic components, prevent-ing oil from migrating into sensitivecomponents and creating hydropho-bic cosmetic powders which do notrun in humid conditions.

Performance of silanesThe durability of any surface modifi-cation is one of the most importantattributes when establishing long-term value in any application.Resistance to rubbing is a very sim-ple but very effective means toassess durability.

Figure 2a compares a traditionalC8F17 silane to the new generationof super hydrophobic PFPE silanesin terms of the effect of rubbing towater contact angle. A second dura-bility test is resistance to UV light

(Figure 2b). The covalent bonding ofthe PFPE silane treating chemical tothe underlying surface is the ration-ale behind its robust durability.

C6Rf silanes are now being devel-oped to replace traditional C8Rf

silanes so as to ensure long-termenvironmental sustainability whilealso maintaining performance. Table3 shows how a new family of C6Rf

silanes has been able to meet theperformance of C8Rf silanes.

ConclusionA new generation of hydrophobicand oleophobic fluorosilicone hybridsurface modifiers has been devel-oped to meet emerging lifestyle-driven needs. The general trend canbe summarised as the need to keepsurfaces clean or good-lookinglonger with minimum effort. Bycombining fluorine and siliconechemistries, highly effective productsare now possible in a wide range ofapplications.

* - Also contributing to this article: Dr PeterHupfield of Dow Corning UK, Eiji Kitaura, ofDow Corning Toray in Japan, Dr Don Kleyer ofDow Corning USA and Drs Yasuo Itami, TetsuyaMasutani and Yasuhiro Nakai, all of DaikinIndustries in Japan

For more information, pleasecontact:Salvatore ReNew Business DevelopmentManagerDaikin Chemical Europe GmbHImmermannstrasse 65dD-40210 DüsseldorfGermanyTel : +49 211 17 92 25-0E-mail: [email protected]: www.daikinchem.de

Daikin.qxp 7/10/08 12:18

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ca 2

mg 2

fe 2

ba 2

pb 2

mn 2

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