elements 30, issue 1 | 2010 - evonik...

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elements30S c i e n c e n e w S l e t t e r

Evonik Innovation Award 2009n e w P r o c e S S e S c a t e g o r y

Nanofiltration Developed to Application Readiness

n e w P r o D U c t S c a t e g o r y

New Functional Silanes for the Construction and Filler Industries

n e w S y S t e M S o l U t i o n S c a t e g o r y

CoverForm®: One-Step In-Mold Scratch Resistance for PMMA

Evonik will focus on its strengths in specialty chemicals. Our Executive Board‘s new business model, endorsed by the Supervisory Board, should make us one of the world‘s leading specialty chemicals companies. Energy will remain within the Group as a largely independently managed affiliate, and Evonik is seeking partners to finance growth projects in this area. Real Estate is being merged with THS GmbH to form a new company that in the medium term will be placed on the capital market as an independent player. The reason for the stronger focus on chemicals is that Evonik alone does not have the financial scope to develop all the three business areas equally and simultaneously. With the new business model, on the other hand, each business area can exploit its growth potential to the fullest. In Chemicals, the emphasis will be on technologies and products that use resources efficiently, contribute to the health and nutrition of the world‘s steadily growing population, and allow growth regions to press ahead with industrialization. Behind these major developments—resource efficiency, health and nutrition, and globalization of technologies—stand attractive markets, in some of which Evonik has already attained leading global positions. We are, for instance, the world‘s largest supplier of chlorosilanes and an important producer of monosilanes, both key components for photovoltaic conversion of solar energy. And in the lithium-ion battery we have in our product portfolio one of the most promising options for the automotive electric drive. Nor do we lack for good ideas on how we can continue to support these major trends in the future. This issue presents three projects that have received our Innovation Award 2009. Our new functional silanes, for example, provide excellent corrosion protection for concrete, among other materials. They therefore allow the concrete cover on rebars to be thinner, thus saving concrete—a construction material whose production is well known to be highly energy intensive. Thanks to our research, nanofiltration is now also possible in organic solvents. Our developers have thus opened the door to more sustainable production in which, for example, solvents can be recovered by energy-saving nanofiltration rather than energy-intensive distillation. Finally, CoverForm®, a system solution devel-oped jointly with KraussMaffei, produces, in a single step, injection-molded PLEXIGLAS® parts with surfaces that are highly scratch-proof and resistant to chemicals. This does away with the need for coating lines, shortens the value chain, and saves time and money. The market has dealt with all three developments very well because they are perfectly in tune with the current “megatrends” and allow efficient utilization of resources—not least because they are the result of a target-oriented innovation process that uses resources efficiently.

Using resources Efficiently

Patrik Wohlhauserchairman of the Board of Management of evonik Degussa gmbH

elements30 evonik science newsletter

e D i t o r i a l

n e w S 23 New binder imparts high gloss and toughness to plastic coatings 24 Thirty years of VESTOPLAST® 24 Evonik acquires Eli Lilly‘s U.S. tippecanoe manufacturing site 25 Joint venture established for manufacture of glass lenses for LEDs B i ot e c H n o lo g y26 Amino acids for specialty applications: bright prospects for white biotechnology n e w S 31 Evonik at Auto Expo India 31 More than 300 VESTAMID® offshore lines in three years 32 e v e n t S a n D c r e D i t S

elements30 | 2010 e vo n i k i n n o vat i o n awa r D 2 0 0 9 4 The winner 6 New Processes category: Nanofiltration developed to application readiness12 New Products category: New functional silanes for the construction and filler industries

n e w S 17 New highly flexible Polyamide 12 for cable conduits 17 € 150 million invested in solar energy and electronics markets of the future

e vo n i k i n n o vat i o n awa r D 2 0 0 9 18 New System Solutions category: CoverForm®: one-step in-mold scratch resistance for PMMA

contents

the cover photo shows a test plant for organic solvent nanofiltration

3elements30 evonik science newsletter

news

evonik industries has completed work on a large complex for base and specialty methacrylates, polymethyl methacrylate (PMMa) molding compounds and thermoplastic methacrylic resins, and has brought the 250-million-euro facility fully onstream after a con-struction period of just two years. From the Shanghai site—the Shanghai chemical industry Park (SciP), an area spanning sever-al square kilometers—the new facility supplies key intermediates for such applications as eco-friendly coatings, concrete additives, and PMMa molding compounds for lightweight and therefore fuel-saving plastic parts for vehicles. Methyl methacrylate (MMa) is a key product of the site. “the global market for MMa is grow-ing by 5 percent per year, and the growth rate in china is signifi-cantly higher even than that. it’s in this boom region that we’re starting up our new facility. thanks to our new integrated produc-tion facility, ours is the only company in the region that can offer nearly all specialty products in this category locally,” said Dr. klaus engel, chairman of the executive Board of evonik industries ag.

New C4 process expands the technology platformMMa is produced by the c4 process, a new process for evonik. For the sake of raw material flexibility, a plant for splitting MtBe, a widely-available basic petrochemical, has been built along with the MMa facility. the plant uses a new process that was devel-oped in evonik’s c4 chemistry Business line, and is being used for the first time in Shanghai. the process increases flexibility and significantly improves the cost situation for MMa production at the site. “with this project we have implemen-ted a unique integrated production con-cept, and with the decision to build a c4 plant for MMa production, we have also considerably expanded our technology platform,” said gre gor Hetzke, head of evonik’s Performance Polymers Business Unit. “with the integrated production facility and the research and development center in Shang hai, evonik is turning into the larg-est supplier of methacry late specialties in china, said Patrik wohlhauser, chairman of

the Management Board of evonik Degussa gmbH, highlighting the significance of this major project. the 25,000 square meter research center houses state-of-the-art laboratories for research, development, application, and technical service, and a pilot plant for polymer technology. evonik employs about 300 people at the SciP site in Shanghai. evonik now has integrated MMa production sites in the U.S., europe and china. „this allows our customers to procure prod-ucts from a single source in each of these regions,“ added Hetzke. Moreover, evonik can from now on offer much shorter delivery times in asia. “in this respect we‘re following our most important global customers who are investing in china, and whom we can now supply here with locally produced materials.” over the next few years, evonik expects steady growth for methacrylates and PMMa molding compounds. among the most important drivers here is the energy efficiency megatrend. “with our products we offer a number of solutions, such as for the solar industry and for weight reduction in the automotive industry. our materials are also increasingly finding application in construction and architecture, and in noise control,” said Hetzke. with its PleXiglaS® molding compounds, evonik is also mak-ing a key contribution to the booming electronics industry in the new generation of leD flat screens. in the area of paints and coat-ings, the company has developed in its viSioMer® monomers important products for waterborne formulations that are environ-mentally friendly—an important future consideration in china.

+++ Integrated production facility in Shanghai fully onstream

Evonik’s new integrated production plant in Shanghai

4 elements30 evonik science newsletter

researchers at inorganic Materials, Performance Polymers, industrial chemicals and Process technology & engineering have won the 2009 innovation award which evonik industries awards once each year to employees in the chemicals Business area for exceptional research performance.

Performance Polymers got top marks for coverForm®, a system solution devel-oped in collaboration with kraussMaffei which enables single-step processing of PleXiglaS® to molded components that boast exceptionally scratch-resist ant and chemical-resistant surfaces.

an interdisciplinary team from Process technology and industrial chemicals successfully employed a newly developed polymer in the first-ever application of organic solvent nanofiltration in a technical chemical process to recover an expensive rhodium-based homogeneous catalyst.

inorganic Materials, for its part, was awarded the prize for its functional new silane systems which, among other merits, provide 35 years of protection against corrosion in cement while containing practically no volatile organic substances.

the three teams accepted their awards – including prize monies of 20,000 euro each – from Patrik wohlhauser, chairman of the Management Board of evonik Degussa gmbH, in essen on December 16. this year’s competi-tion for the coveted trophy drew submissions from a total of 22 teams. Six of them presented new products, ten of them new or improved processes, and six others new system solutions. the jury, comprising in-house and external experts, assessed the projects based on defined criteria. For one thing, the entries had to re -present new developments which were either

market mature or already launched on the market. they also had to offer eco-nomic as well as ecological benefits, and they were required to possess evident value for society. Marks were additionally given for originality and creativity.

Evonik Innovation Award

2009


Category New Processes

Nanofiltration developed to application readiness

Stefan DreesDr. Robert FrankeDr. Hans-Gerd LuekenPatrick MuhlackDr. Markus RudekHermann-Josef Schulte-AlthoffDr. Klaus-Diether WieseIndustrial Chemicals Business Unit

Dr. Goetz BaumgartenChristian LingnerMarkus PriskeProcess Technology & Engineering Service Unit

Category New Products

New functional silanes for the construction and filler industries

Dr. Christine FliednerDr. Manuel FriedelDr. Sabine Giessler-BlankDr. Heidi GrönSpomenko LjesicReiner StörgerDr. Kerstin WeißenbachInorganic Materials Business Unit

Category New System Solutions

CoverForm®: one-step in-moldscratch resistance for PMMA

Dr. Klaus AlbrechtRudolf BlassArne SchmidtSven SchröbelDr. Dominic StörkleChristian EberleDr. Thorsten GoldackerKlaus KoralewskiWerner HößPerformance Polymers Business Unit

nanofiltration Developed to Application Readiness

n e w P r o c e S S e S c a t e g o r y


nanofiltration Developed to Application Readiness

C

with the aid of a newly developed polymer, an interdisciplinary team consisting of members from Process technology and industrial chemicals—two of evonik’s units—has succeeded in using organic solvent nanofiltration for the first time in a technical process for recovering a costly homogeneous catalyst. For this notable technical and commercial breakthrough, the team has received the innovation award 2009 in the new Processes category.


atalytic processes are of paramount importance in the chemical industry; more than 90 percent of all chemical products undergo a catalytic process in at least one stage of production. The reasons are

many and various: Catalysts reduce energy consumption, save resources, and minimize costs, particularly if they can be recovered and reused. Homogeneous catalysis offers spe-cial advantages. In this case, the catalyst and starting mate -r ials are in the same phase, and the active centers of the catalyst are therefore fully available for catalysis. For this reason, homogeneous catalysts are often more active and selective than heterogeneous catalysts. The high selectivity, apart from their commercial advant ages, contributes to pro-tecting the environment. These properties make homogeneous catalysis of great interest to the chemical industry. In practice, however, chem-ists often resort to heterogeneous catalysts, for the follow-ing two reas ons. Homogeneous catalysts are often in the form of metal complexes, with a central transition metal ion and ligands through which the catalytic properties can be regul ated. The catalyst is susceptible to poisoning, and in pract ice significant catalyst deactivation may therefore oc-cur during the reaction. Separating the homogeneous catalyst from the reaction mixture presents a considerably more difficult problem. The products formed must usually be separated from the catalyst under conditions that do not damage the sensitive catalyst systems. This means that homogeneous catalysts can be re-covered from the reaction mixture only with difficulty.

e v o n i k i n n o v a t i o n a w a r D 2 0 0 9

The result is product contamination and high costs aris-ing from catalyst losses: Homogeneous catalysts often con-tain metals from the platinum group of the periodic table, including precious metals such as rhodium, palladium, and platinum itself, which significantly raises costs, particularly when raw materials prices are high. The specific ligands required, which have a major influence on selectivity, are usually also prohibitively expensive. According to experts' estimates, separation accounts for 40 to 70 percent of production costs when homogeneous catalysis is used. Given these costs, chemists continue to search for extremely gentle alternatives to the distillation that is currently widely used. One promising approach here is organic solvent nanofiltration.

Nanofiltration already in commercial use for water treatment

Nanofiltration is an established membrane process in water treatment for removal of multivalent ions. In its rejection characteristics, it ranks between reverse osmosis and ultra-filtration. Processes of this type are already being used for water softening and in the process industry for desalination of dyes and lactose recovery. Membranes suitable for water-borne systems cannot be used in organic solvents, however. The only commercial system for organic solvent nanofiltra-tion so far implemented is the MAX-DEWAX process used in Exxon Mobil's Beaumont, Texas, refinery since 2001. This recovers hexane, which is used to dewax lube oil, from lube oil/solvent mixtures at low temperatures. In certain important organic syntheses, organic solvent nanofiltration offers a new option for gently separating the homogeneous catalyst systems. The reactions concerned in-clude Suzuki coupling, a palladium catalyzed cross-coupling between organoboronic acids and aryl halides; metathesis, in which substituents at double or triple bonds are formally exchanged in the presence of catalytically active >>>

Evonik‘s test plant at the Marl Chemical Park for recovery of homogeneous catalysts by organic solvent nanofiltration

+


Membrantechnik GmbH in Rheinfelden, the Technical University of Darmstadt, and the University of Rostock. As one of the model processes, the developers used a hy-droformylation reaction catalyzed by a rhodium complex (fig. 1). In this process, thermal separation of the longer-chain aldehydes is a problem for the sensitive catalyst sys-tem, which contains carbon monoxide in addition to ligands. The products must be removed under high vacuum, so that the partial pressure of carbon monoxide approaches zero. As a result, carbonyl groups are released from the rhodium complex, leaving vacant coordination positions that are oc-cupied by other rhodium atoms. This leads to progressive clustering that deactivates the catalyst. The goal of the BMBF-funded project was therefore to investigate whether and how organic solvent nanofiltration could be used as an alternative and to make this option com-mercially useful. This would allow the separation to be car-ried out at significantly lower temperatures so that catalyst activity could be retained. The BMBF-funded project succeeded in showing that or-ganic solvent nanofiltration is suitable for separating sensi-tive homogeneous catalysts of complex structure even from high-boiling components. Separation is thus achieved with-out deactivation of the catalyst complex by progressive clus -t ering, and losses through catalyst decomposition are avoid-ed. The project participants have also demonstrated that the process can be transferred from the bench scale tube to a test reactor system. As a basis for further development at Evonik, membrane systems already available on the market have been screened.

transition metal compounds; and hydroformylation. This last reaction is a reaction of olefins with a mixture of hydro-gen and carbon monoxide, known as syngas, to form alde-hydes. This synthetic pathway, discovered in 1938 by the German chemist Otto Roelen, is now one of the most im-port ant homogeneously catalyzed reactions, the catalysts in this case being rhodium complexes. Aldehydes are in de-mand as versatile intermediates in the production of various families of compounds. These include principally alcohols and diols as well as carboxylic acids, esters, and amines, which are also of great industrial importance.

Wanted: membrane materials that are stable in organic solvents

The reason that nanofiltration has not been used so far in production processes of this kind is that most membranes are not stable in organic solvents and cannot achieve the re-quired separation efficiency. Since they do, however, offer enormous potential in chemical synthesis—for energy-effi-cient solvent recovery as well as in the recovery of homoge-neous catalysts—a project funded by the BMBF (the German Federal Ministry of Education and Research) studied organic solvent nanofiltration until mid-2009. Jointly with external partners, researchers from Evonik's Industrial Chemicals Business Unit and Process Technology & Engineering Service Unit have brought the nanofiltration process to readiness for industrial application. The partici-pants in this successful project, which ran for four years, were the GKSS Research Center in Geesthacht, GMT

Evonik uses homogeneously catalyzed hydroform-ylation as one of the model processes for organic solvent nanofiltration. The thermal separation of high-boiling solvents is a fundamental challenge here because the sensitive catalyst system can be deactivated in the process

Figure 1

R + +CO H2

Catalyst

Ligand

R

H

O

H

linear

erwünscht

branched

unerwünscht

H

H

O

+

Olefin

Aldehyde

Vaporizer

Catalystrecirculation

High boiler ejectionand catalyst losses

H2, CO

Rea

ctor



cause it is highly stable in most organic solvents. Additionally, the GKSS Research Center modified the membrane to further improve its properties. For the nanofiltration after the reactor, the following pre conditions must be fulfilled. An active catalyst complex has to be present for separation of the rhodium. The mem-brane rejects the catalyst complex to the maximum possible extent while the solvent passes through unhindered. The membrane has to prove stable in olefins, paraffins,

Polyimides (PI) and silicones have been found to be rather suitable as membrane materials. Appropriate systems using these materials are offered by various producers in Germany, the U.K., and the Netherlands. The membranes are usually constructed in three sections consisting of a nonwoven base, a porous supporting layer, and the actual functional nanofil-tration membrane (fig. 2). After the available membranes were tested, a silicone-based membrane was found to offer the best solution be- >>>

Figure 2Preliminary tests showed that a silicone-based membrane is best suited for organic solvent nano-filtration: It is permeable to high boilers and can in principle reject the catalyst. However, the memb-rane swells in the course of time, thus becoming increasingly permeable to the catalyst. The dia-gram shows how the rejection of the membrane shifts in the direction of higher molecular weight as the swelling increases, an effect that is undesir-able. The developers solved this problem by mo-d ifying the membrane material so that it can no longer swell

Below: SEM micrograph of a silicone-based organic solvent nanofiltration membrane

Source: GKSS Research Center, Geesthacht

Laboratory system for organic solvent nano-filtration (left). At the core of the system is the membrane module (middle photo). The photo on the right shows that the system works: After organic solvent nanofiltration the reaction solution has become colorless

Day 1 Day 10 Day 100

Rejection [%]

100

50

Molecular weight (high boilers)

90% Rejection

Swelling


Figure 3The catalyst rejection method investigated in the test plant has proven to be technically feasible. Since 2006, the membrane material has been optimized by modification so that catalyst rejection has now increased to more than 99 percent. The photo on the right shows a membrane module for organic solvent nanofiltration

Evonik has proven—initially in a laboratory setup and later in a test plant—that organic solvent nano-filtration works, and not just on the labor a-tory scale

Olefin

Aldehyde

Vaporizer

Catalystrecirculation

High boiler ejection and

minimal catalyst losses

H2, CO

Rea

ctor

Organic solvent nanofiltration

Membrane module

90

100

80

70

60

50

40

30

20

10

0

Catalyst rejection [%]

2006 2008 2009



to introduce a completely new class of polymers in membrane applications that allows organic solvents to be separated rather efficiently (fig. 4). The special feature of the new po-lymers is a structure that gives them intrinsic microporosi-ty, which results in extraordinarily high membrane perfor-mance in con junction with especially efficient separation, as is required in advanced recovery processes. With this pioneering development, the researchers have paved the way for a more effective separation technology in the process industry allowing, for example, solvent recov-ery by energy conserving nanofiltration instead of energy-intensive distillation. l

alde hydes, and alcohols. Furthermore, its temperature stab-ility must be as high as possible because the reaction compo-nents are extremely viscous at low temperatures and mass transfer would then be very slow. In the test plant for organic solvent nanofiltration, the fil-trate, consisting mainly of the reaction product, was removed from the system. The rhodium-ligand complex was rejected by the membrane and then concentrated. Along with fresh starting material, the catalyst concentrate was then fed back into the reactor. Analysis of the kinetic data shows that membrane separation has no negative impact on catalyst activity. It has also been proven that rhodium rejection in creases with increasing quantities of permeate because the membrane is partially reversibly compacted, which fur ther improves separation efficiency.

Rhodium recovered virtually quantitatively

The most important finding is the technical feasibility of the process. The catalyst remains not only stable but also active under the selected conditions. As a result, the valuable rho-d ium can be recovered virtually quantitatively, thanks to na-no filtration, and used in the following reaction cycle (fig. 3). Evonik has found that nanofiltration is a robust and stable process, as was definitively proven by the successful opera-tion of the test plant. The company will therefore use this method as a platform technology, primarily for further de-veloping homogeneous catalysis with its special advantages. The team, which has now been awarded the Innovation Award, has built on the findings of the BMBF-funded project

DR. ROBERT FRANkEindustrial chemicals Business Unitr&D Manager+49 2365 [email protected]

DR. MARkUS RUDEkindustrial chemicals Business UnitPlant Manager+49 2365 [email protected]

DR. GOETz BAUMGARTENSenior Manager, Membrane Processes Process technology & engineering Service Unit +49 2365 [email protected]

CONTACT

Figure 4On the basis of the results of the BMBF-funded project, a com-pletely new class of polymers possessing intrinsic microporosity has been developed for membrane applica-tions in conjunction with Evonik

new Functional Silanes for the construction and Filler industries

n e w P r o D U c t S c a t e g o r y


Functional silanes open up new applications and improve existing ones in the construction and filler industries. as a starting point for their production, evonik uses a side-stream from the synthesis of organofunctional silanes.

t the boundary between Berlin‘s Charlottenburg and Tiergarten districts stands the Charlottenburg Gate, an ornate neo-baroque structure dating from the early twentieth century. Situated between Ernst-

Reuter-Platz and the Siegessäule on the Strasse des 17. Juni, it forms a counterpart to the Brandenburg Gate on the op-posite side of the Tiergarten. Following the extensive resto-r ation of the actual structure last year, the Berlin restoration firm Opus is now taking in hand the two 22 meter high candelabra that stood on the Charlottenburg side of the gate before they were destroyed in the Second World War. Be-fore the year ends, the two columns will be restored to their previous splendor. Originally of tufa, the candelabra will be reconstructed by Opus using a concrete mix that allows rep-lication of the ocher color of the stone. And the concrete also con ceals other surprises: An oligomeric alkylsilane that Evonik has developed for the construction industry will, by its water-repellent action, ensure the durability of the restored candelabra. Employees of the integrated silicon production facility in the Inorganic Materials Business Unit have succeeded in developing oligomeric alkylsilanes from a side stream in the synthesis of organofunctional chlorosilanes to the extent that they open up entirely new possibilities for the construc-tion and filler industries. For this achievement the team has now received Evonik‘s Innovation Award for 2009 in the New Products category. The Inorganic Materials Business Unit is a globally active supplier of functional silanes, with a total of four production sites in the Europe, North America, and Asia Regions. The business unit works in close conjunction with strategic cus-tomers and develops together with them optimized silanes that help open up new market opportunities. Evonik pools product know-how in its Protectosil® and Dynasylan® functional silanes. Protectosil® offers solutions for water repellents, protection against graffiti and corrosion, and surface protection for a variety of materials including con-crete, sandstone, granite, and stucco. The Dyna sy lan® >>>

AThe Charlottenburg Gate in Berlin. Protectosil® 851 was used in the restoration of the gate and candelabra (not shown in the picture.) The water-repellent concrete additive was the only product that could meet the rigorous requirements on reduc-tion of water absorption, the processability of the resulting mixture, and the visual appearance of the finished concrete

new Functional Silanes for the construction and Filler industries




brand, on the other hand, has for more than 50 years stood for silanes that help improve product properties in a widely diverse range of industries, from paints and coatings through sealants and fillers to pharmaceuticals.

Wanted: water-repellent building materials that are easily processed

The construction industry needs high-performance chemi-cals that are easy to process at construction sites. For a wide variety of substrates, water repellent action is the most important requirement because this is the only way of pre-venting corrosion in reinforced concrete, alkali-silica reac-tions, or sulfate attack. Corrosion of rebars is one of the major causes today for failure of concrete structures. A tragic example from the U.S. is the bridge carrying the Interstate 35 Highway in Minnesota, which collapsed on August 1, 2007. The filler in-dustry also needs water repellents as cost-effective but high performance dispersants that should have a very low con-tent of volatile organic compounds. These are used primari-ly for manufacturing window frames and plastic films. The oligomeric alkylsilane that Evonik obtains from a synthesis of organofunctional chlorosilanes is the base prod-uct for the new development, which allows new and im-proved applications in the construction and filler industries. The employees of the business unit have produced three grades, which have different physical properties; there is also one customizable grade.

Low volatile organic compound content

The products are Dynasylan® 9896 and Protectosil® 266. Dynasylan® 9896, aimed at the filler industry (fig. 1), has a significantly lower volatile organic compound content than the monomeric silanes that are frequently used as disper-sants. This is important for processing and also, from a broad er viewpoint, because of increasing public concern in both Europe and the U.S. about hazardous gas emissions from organic compounds, with intense political debate on appro priate limits. Dynasylan® 9896 has a high boiling point and is thus suitable even for applications where high safety require ments must be met. The surface of a treated filler can be mod ified even at relatively high temperatures without affect ing the water-repellent action. Protectosil® 266 on the other hand is an oligomeric alkyl-silane serving as an impregnating agent for absorbent min-eral facade construction materials. It is competitive with the silicone-based products that have so far dominated this mar-ket segment. As an aqueous emulsion, the product has the names Protectosil® WS 610 and WS 630, and as a powder Protectosil® DRY CIT. All the three are virtually free of volatile organic compounds. They allow the concrete cover of rebars to be thinner; this reduces the required quantity of concrete, a construction material whose production is known to be highly energy intensive.

35 years of corrosion protection for concrete

As early as 2008, Evonik received an award for Protectosil® DRY CIT at Deubau, Germany‘s most important trade show for the construction industry. The organic sheath of the powder system dissolves in the cement mix, releasing the active components where they are needed. The components bind covalently to the concrete in a chemical reaction, which explains the remarkable durability of the corrosion protec-tion (fig. 2). Tests confirm that Protectosil® DRY CIT re-mains effective for at least 35 years (fig. 3,4). In contrast, the corrosion control formulations available on the market are often good for only a few years. >>>

Figure 1Effect of Dynasylan® 9896 for waterproofing of fillers as observed in the model system of titanium dioxide in paraffin oil, compared with untreated titanium dioxide and titanium dioxide treated with silicone or octylsilane. The filler treated with Dynasylan® 9896 is distinguished by very low viscosity and excellent dispersibility. This allows high filler content and the finished structure, such as a window frame, has a smooth surface

Titanium dioxide untreated treated: 0.2% silicone treated: 1% octylsilane treated: 1% Dynasylan® 9896

Viscosity (Brookfield viscometer) [mPas]

Figure 2Protectosil® DRY CIT bonds covalently to concrete, ensuring long-term corrosion protection

Spindle speed [rpm]

100,000

10,000

1,000

100

10

100101

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Substrate, e.g. concrete

Unprotected concrete

10mm depth 30mm depth 50mm depth

Current [µA]

Corrosion measurement in untreated concrete and in concrete treated with Protectosil® DRY CIT. Sensors were inserted in a concrete block of edge length 15 cm, at depths of 10, 30, and 50 mm (figure above)

The sensors were connected through an external resistance to a counter electrode, allowing measurement of corrosion current and the elec-trical resistance of the concrete. In each case, the concrete block was immersed for two days in a unimolar NaCl solution and then dried for five days; the entire test extended over 520 days

In the unprotected concrete the sensors corrode after a short time as is seen from the development of corrosion current, even when the concrete cover is thick (figure above right)

By contrast, concrete protected with Protectosil® DRY CIT shows no signs of corrosion over the entire period (figure middle right). The duration of the tests corresponds to corrosion protection for at least 35 years of outdoor exposure

The results are collected in the table

Figure 4Important properties of fresh concrete such as flowability and bulk density remain unchanged upon addition of Protectosil® DRY CIT. Only the compressive strength of fresh samples shows a slight reduction, which, however, disappears as the hydration reaction progresses. After 90 days the differences are usually barely measurable

Figure 3

Electrodes Sensors Cl –

50 mm

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Concrete protected with 4 wt.% (relative to concrete weight) of Protectosil® DRY CIT

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Current [µA]

Numbers of ponding days

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Depth

Untreated concrete

Concrete treated with 2 weight percentProtectosil® DRY CIT

Concrete treated with 4 weight percentProtectosil® DRY CIT

Water-uptake

[g]

39.3

13.5(66%

reduction)

11.6(70%

reduction)

Chloride content[weight percent relative

to concrete weight]

15-30mm

5.78

2.22(62%

reduction)

0.46(92%

reduction)

Resistance[kOhm]

10mm

0.417

2.3

128

30mm

0.312

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185

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reduction)

1.55(75%

reduction)

Concrete without Protectosil® DRY CIT with 2 weight percent Protectosil® DRY CIT (relative to concrete weight) with 3 weight percent Protectosil® DRY CIT (relative to concrete weight)

Compressive strength

[N/mm2]

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020 40 60 80 100




The fourth grade of the oligomeric alkylsilane is a custom-izable solution: Protectosil® 60 SK can be rapidly adapted for new customer requirements, for example, by the use of sui-table catalysts, so that the water-repellent action of the pro-duct can be fully developed even on substrates of lower al-kalinity (fig. 5). Ever since the market launch of the oligomeric alkylsi-lanes, the products have enjoyed increasing popularity among customers, thanks to their excellent property profile. In none of the grades could the oligomeric alkylsilane be used directly after its generation as a by-product in the syn-thesis of organofunctional chlorosilanes; various refining steps and extensive tests were necessary. With the powder grade, for example, a problem arose on mixing the product with concrete, when large quantities of air were introduced; the project team had to find a suitable defoamer that could be added to the powder. Silane systems have long been used for their water repel-lent action. They also have excellent corrosion inhibiting properties. Until now, however, they have always had the disadvantage of a high volatile organic substance content due to the alkoxy groups of the silanes. With their oligomer-ized alkylsilanes, the project team has succeeded in reduc ing these unwanted emissions by up to 85 percent, making an important contribution toward a healthier environment. l

DR. MANUEL FRIEDELapplied technology Silanes for Building Protectioninorganic Materials Business Unit+49 7623 [email protected]

CONTACT

The Buda Castle in Budapest (Hungary) was restored in 2008. Since then, Protectosil® WS 630 has been protecting the walls against moisture

Figure 5The water-beading effect of Protectosil® 60 Sk remains intact even after 470 hours of artificial weathering

By contrast, the effectiveness of a commercially available water repellent decreases significantly over the same period

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+++ Verbundanlage in Schanghai komplett in Betrieb genommen


news

+++ New highly flexible Polyamide 12 for cable conduits

evonik industries has extended its product range of flame-retardant polyamide 12 compounds for cable conduits and cable protection hoses. with veStaMiD® eX9203 black, a highly flexible molding compound, the company is responding to increasingly tough require-ments in the electrical and cable industries and is supplementing its extensive portfolio of halogen-free flame-retardant plastics. veStaMiD® eX9203, which is colored black, is distinguished by excellent fire-retardant properties and a high oxygen index. with an elastic modulus of 770 MPa, it is highly flexible. this outstandingly flexible and the highly impact-resistant material keeps on working even at temperatures as cold as –50°c. Halogen-free flame-retardant cable conduits and cable protection hoses are in demand, partic-ularly for dynamically highly stressed components, as in rail vehicles, industrial plants, and mechanical engineering.

+++ € 150 million invested in solar energy and electronics markets of the future

in november 2009, evonik industries and its partner taiyo nip-pon Sanso corporation (tnSc) in yokkaichi (Japan) laid the cor-ner stone for a future-oriented project to use environmentally friendly solar energy. a traditional Shinto ceremony consecrated the ground for the beginning of construction on an integrated production plant for monosilane and aeroSil®, the centerpiece of the project, for which a total volume of € 150 million (¥20 bil-lion) has been earmarked. commissioning is scheduled for 2011. tnSc and evonik signed the agreement to implement the project in May of this year, despite the worldwide economic crisis. “By beginning construction on time evonik is pressing ahead with this significant investment in solar energy and electronics, both mar-kets of the future, and is taking a further step in the attractive

climate protection trends are important growth drivers for our business,“ said engel. He added that with its commitment in yokkaichi, the evonik group is taking the opportunity in this rapidly develop ing market to make a substantial contribution to climate protection through its innovative products and services. evonik has now signed a long-term supply agreement for mo-nosilane with tnSc, one of the foremost global distributors for industrial and specialty gases, which includes silanes, and supplier to major customers in the electronics industry in asia for many years. Silanes are key components in the manufacture of ultra-pure silicon, an important raw material in the solar and electronics in-dustry. the silicon tetrachloride generated during monosilane production in yokkaichi is processed into aeroSil® and marketed

Ulrich Sieler, President Evonik Degussa Japan, at the Shinto ceremony. Electronic-quality mono-silane is needed for the manufacture of flat screens, among other applications

asian market,“ says Dr. klaus engel, chairman of the executive Board of evonik industries ag. evonik is already one of the worldwide leading producer of chlorosilanes and a major producer of monosilane—both key components for opening up the solar energy market. there is no end in sight for the worldwide solar boom. Based on forecasts, the world market for monosilanes alone is set to grow an annual 20 percent, on average, by 2020. „the big energy efficiency and

separately for applications in plastics, paints, and coatings, for ex-ample, as well as adhesives and sealants. evonik developed the monosilane production process itself and is already running a plant in rheinfelden (germany). the yok kai chi plant allows the company to produce electronics-grade monosilane for applications in thin-film photovoltaics, flat screens, and semiconductors electronics, which are strong growth areas, especially in asia.

CoverForm®: one-Step in-Mold Scratch resistance for PMMa

n e w S y S t e M S o l U t i o n S c a t e g o r y


in an unusual collaboration, evonik industries and machine manufacturer kraussMaffei have set a milestone in plastics processing. their jointly developed, single-step coverForm® system solution produces injection-molded PleXiglaS® parts with highly scratch- and chemical-resist ant surfaces, dramatically lowering production costs. For this achievement the developers of the process have now received the evonik innovation award in the new System Solutions category. experts in the trade are no less amazed: at the Materialica trade show in october 2009, coverForm® won both the Materialica Design & technology award and the “Best of” award in the Surface & technology category. in Darmstadt (germany) evonik established a competence center exclusively for the technology; since november 2009, customers and others have been getting a closer view of the technology and performing trial runs of their own samples.

Figure 1Comparison of conventional process, consisting of injection molding followed by coating of the part in a coating line (above), and the CoverForm® process. The latter reduces the number of process steps from 14 to four

Injection molding process

Inspection upon delivery

Injection molding

QA-inspection Transport

Coating process

Applyingprimer

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QA-inspection

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CoverForm®

Inspection upon delivery

Injection moldingCoverForm®

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Final assembly

CoverForm®: one-Step in-Mold Scratch resistance for PMMa

A


mobile phone display, the panel on a household appliance, and the speedometer cover in a car all have something in common: They are made of transparent plastics. Mechanically, their surfaces

are subjected to tough punishment. Chemically, they are often challenged by cleaning agents and hand creams. If the plastic fails to resist attack, transparency, and thus function, are undermined. For PLEXIGLAS® parts to stand up to these kinds of tough conditions, they are coated with a scratch- resistant film that also provides high resistance to chemicals. After the injection molding machine has made the part, it typically goes straight to the coating line. Taking into ac-count quality checks and transport, the process includes no fewer than 14 steps from molding compound through injec-tion-molded part to the finished and coated plastic part for final assembly. CoverForm® technology, however, reduces the steps in this value chain to just four: incoming inspec-tion, CoverForm® injection molding, quality control, and final assembly (fig. 1). All four steps occur in an in-line pro-cess and, what is more, in the same machine, which saves time, costs, and space. Moreover, the plastic surfaces thus produced are in many cases more scratch resistant than tho-se that have been coated in the traditional way.

From concept…

The concept of CoverForm® was developed by scientists at Evonik‘s Performance Polymers Business Unit nearly four years ago. They wanted to coat the injection molded part right in the injection molding machine, as in the RIM (reac-tion injection molding) process in polyurethane processing. Searching for a suitable partner, Evonik found the right


people at KraussMaffei AG in Munich. At the time, this machine manufacturer was further developing the RIM tech-nology to mold microstructures on optical media (Blu-ray DVD) using low-viscosity fluids, and was on the lookout for a suit able material.

…to joint product in just two years

After only one year, the collaboration yielded an initial con-cept study, which both companies introduced jointly at the K 2007 plastics trade show under the name CoverForm®. The new technology attracted enormous interest in areas as diverse as automotive engineering, electronics, and house-hold goods. Spurred by this success, the two partners readied the concept to mass-production within a few months. One tech-nical challenge was sealing the entire system, for example.

Integrated solution

All problems were solved, and Evonik and KraussMaffei jointly launched the technology on the market as a system solution under the name CoverForm® in 2009. This consists of the injection molding machine, PLEXIGLAS® cf molding compound, the Reactive Liquide cf 30A reactive system for coating, and the part-specific mold. The CoverForm® process requires special PLEXIGLAS® molding compounds developed by Evonik, which are desig-nated by the suffix “cf,” and their additives must satisfy cer-tain specification limits. The solvent-free reactive system consists of two components based on multifunctional (meth)acrylates. The injection device meters the reactive >>>

The CoverForm® Competence Center in Darmstadt (Germany)


Streamlining adds value

The CoverForm® process thus incorporates the reactive steps into the injection molding process. Production cycle time is therefore longer than for “ordinary” injection mold-ing because the machine is occupied by each molded part for a longer period; this reduces throughput and appears at first sight to be an economical disadvantage. But if viewed as a single whole comprising both injection molding and coating, the process proves to be unusually efficient because it reduces the number of process steps necessary from 14 to four. CoverForm® saves plastics processors the high capital costs of an additional coating line. Those who lack the finan-cial resources for their own coating line, and have as a result been outsourcing the production of molded parts, can now save themselves the logistical effort and expense involved. Both benefit overall from the new technology, and even the

solution from a small storage flask into the mold with micro-liter accuracy. Curing is done thermally in the CoverForm® mold and also by UV radiation after removal from the mold. In the actual process (fig. 2), the mold closes at the start of the cycle. As is usual for injection molding, the plastified PLEXIGLAS® molding compound is injected into the cavity. While the melt is cooling and solidifying to form the molded part, the mold continues to exert pressure on the melt in the cavity. The cavity then expands, the injector meters in the reac-tive solution, and the mold compresses the cavity once again. Crosslinking of the reactive solution is initiated under pres-sure by a brief heat pulse, and the acrylate system is cured on the surface of the molded part. The mold is then opened and the robot removes the molded part and places it on a conveyor belt. Under UV light the coating film is then com-pletely cured in-line on the belt in a matter of seconds.

Figure 2The CoverForm® process

Figure 3Comparison of thermal curing systems, UV curing systems, and CoverForm® coating

Thermal systems

Crosslinking siloxanes

Heat curing

Contain solvents

Offline process

Efficiency 20-95%

CoverForm®

Multifunctional acrylate

Curing by heat and UV-radiation

Free from solvents and siloxanes

Inline process

Efficiency 99%

UV-systems

Multifunctional acrylates, often modified with siloxane

UV-curing at room temperature

Contain solvents

Offline process

Efficiency 20-95%

Injection ofPLExIGLAS®

Compression and holding

pressure phase

Expansion of mold cavity

Injection of reactive system

Cooling phase

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phaseCooling of

cavity

Opening of mold

Removal of molded part

Closing of mold

Reaction processInjection molding process Injection molding processReaction process



smaller plastics processors can now produce cured PLEXIGLAS® cost effectively in their own machines by using the CoverForm® system solution. The injection molding machine can also be used for con-ventional injection molding if, for example, parts with a scratch resistant coating are not required. It is even possible to run two production lines for a single part: a higher grade line delivering a coated surface and a second, less expen-sive, one without this feature. Because the CoverForm® machine allows fast batch changes, moreover, the customer can respond to the market flexibly—and, because he has the complete process under his roof, at no great expense. The CoverForm® injection molding machine also scores on its footprint. Thanks to its compact structure, it needs no more than 100 square meters of space, as opposed to the 1,000 square meters necessary in the conventional produc-tion process for injection molding machine and coating line.

Invisible curing

CoverForm® coating has been designed as an in-line process. The specially developed reactive solution is solvent- and siloxane-free, and is metered to microliter accuracy. This means that it is not necessary to flood the mold or recycle excess coating material—unlike conventional thermal coat-ing systems. The coating is crosslinked and cured thermally as well as by UV radiation. Thermal crosslinking alone achieves an efficiency of 95 percent, which UV curing then increases to 99 percent (fig. 3). The coating thickness is nor-mally about 20 µm but can be varied between 10µm and 50µm. The pilot plant mold produces 100mm x 100mm sample sheets of various thicknesses, which can be used in all the usual tests for scratch resistance and chemical resistance. To get a more accurate picture of the surface properties, Evonik and KraussMaffei’s scientists subjected the samples to various scratch resistance tests and compared them with other PMMA surfaces—PLEXIGLAS® 8N and PLEXIGLAS® 8N acrylate-based UV coating—and with siloxane coated poly-carbonate. Hardness tests and suntan lotion and hand cream tests show that the CoverForm® coating is extremely resistant to scratch ing and chemicals. In composite tests such as the ball indentation test and the alternating climate test, CoverForm® has proved notably superior to other coating systems. The reason is that no adhesion promoter is needed for CoverForm® coat ing because compound and coating are precisely matched to each other. This special feature of the CoverForm® coating is very clearly seen in a scanning electron micrograph of a cryofrac-ture in a workpiece broken after liquid nitrogen cooling. The PMMA substrate and the CoverForm® film have the same refractive index of 1.49. There is therefore no deflec-tion of the light beam at the interface between substrate and coating film. In micrographs, the film is not distinguished from the substrate, and is “invisible.” By contrast, a com-mercial-grade polysiloxane coating on polycarbonate is vis-ible on a cryofracture; the phase boundary is clearly >>>

CoverForm® put to the test

Pencil hardness test. with a pencil hardness of 7H, the coverForm® coating of PleXiglaS® 8n cf is harder than PleXiglaS® 8n (5H) and PleXiglaS® 8n with acrylate-based Uv coating (6H), and many times harder than polycarbonate with a siloxane coating (H).Taber test. the coverForm® coating yields good results comparable to those for conventional coating systems. Scratch hardness test (Erichsen 413). the coverForm® coating resists damage caused by the scratching tip at low as well as high loads, whereas the other systems become damaged.Sand trickling test. the coverForm® coating here yields results as good as those for the crown glass used as the standard.Ball indentation test. the coverForm® coating yields good results similar to those for the two other PleXiglaS® samples: the coverForm® composite, consisting of a hard film on a hard undercoat, withstands the imposed stress. By contrast, the hard siloxane coating on the soft polycarbonate undercoat ruptures under pressure, similarly to a thin glass plate on a sponge.PV 3964 suntan lotion and hand cream test. the coverForm® coating does not react at all with the creams over a period of 24 hours at 80°c in a drying cabinet. the surface shows no damage and the scratch resistance remains entirely unaffected. By contrast, the surfaces of most plastics and coatings are damaged in this test. Alternating climate test. the coverForm® coating withstands a large number of load cycles at various humidities and temperatures between –40°c and 95°c.

The scratch hardness test (Erichsen 413) impressively shows how mechanically durable CoverForm® parts can be

PLExIGLAS® 8N PLExIGLAS® 8N cf with CoverForm® PLExIGLAS® 8N cf with acrylate-based UV coating Polycarbonate with polysiloxane coating

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8N7N6N5N4N3N2N1N0.5NBearing force [N]


Even more surface functionality

The CoverForm® technology creates PLEXIGLAS® molded parts and directly produces—in-line and with no change of mold—a scratch- and chemical-resistant coating. The only restrictions are that the component to be coated must be moldable and can be coated only on one side. Potential application areas open up wherever high quality coatings are required that must be resistant to scratching and wear arising from contact with hands, fingers, or hand creams. Examples include automobile interior parts such as speedometer and switch covers and panels, watch and clock glasses, covers of household gadgets, mobile phone and smart phone displays, eyeglasses, and sunshades. Other reactive systems with new surface functionalities are being developed, with a focus on nonreflecting and elec-trically conducting surfaces. l

seen in this case. When a load is applied, the adhesion pro-moter ruptures in the middle; in other words, it continues to ad here to both substrate and coating film, resulting in what is known as a cohesive fracture. Due to the different refrac-tive indices of the polycarbonate and the coating film, such parts always have a superficial iridescent shimmer to them, which is inherently absent in CoverForm®.

CoverForm® for hands-on innovation: The Competence Center in Darmstadt

Encouraged by the extraordinarily high demand from current and prospective customers, Evonik Industries and KraussMaffei AG opened a Competence Center in Darmstadt in November 2008, allowing them to check out CoverForm® for themselves. Customers can have samples coated and ob-serve the process in action. During the discussion, the CoverForm® machine, positi-oned near the meeting table, produces samples that custo-mers can take back to their own labs for testing. In this way, customers see first hand that the CoverForm® process is re-liable and simple enough for them to use, and by no means exclusive to chemical industry experts. Training classes and exclusive projects with custom ers are also available. In addition to providing advice and training, the Com pe-tence Center also serves as a test center for carrying out ma-terials tests and as a platform for further development of the reactive system.

SVEN SCHRöBELManager, Business Development, automotive & Surface DesignPerformance Polymers Business Unit+49 6151 [email protected]

CONTACT

The injection molding machine designed exclusively for the CoverForm® process

+++ Verbundanlage in Schanghai komplett in Betrieb genommen


news

+++ New binder imparts high gloss and toughness to plastic coatings

electronic gadgets are right at the top of consumers’ wish lists, and not just for christmas! those with housings finished in luxu-rious piano black are currently in vogue. Until recently, however, gadgets with their glossy plastic skins suffered from a serious de-ficit. their surfaces were particularly sensitive and almost impos-s ible to clean without damaging the coating. evonik industries has now solved this problem with a new methacrylate resin. it goes without saying that electronic devices like cell phones, MP3 players, and flat-screen tvs have to function reliably and well, but, at the same time, they also need to look polished and chic and embody the latest styles, because a sophisticated appear-ance is a sign of quality—and helps the item sell itself. a growing number of buyers think it important, for example, that a flatscreen tv blend harmoniously into a contemporarily furnished living room, yet stand out as an art object, a conversation piece on ac-count of its elegant design. For flat-screen tvs, the trend these days is classic black—to be sure, piano black—a glossy plastic coating that conveys virtu-ally the same quality as an expensive concert grand piano. nearly all major television set manufacturers are clearly partial to piano black in their product range, aware as they are that the appear-ance of a tv set, in addition to the electronics it houses, plays a major role in buying decisions.

The irreconcilable reconciledthe problem, however, is that common glossy plastic coatings are relatively susceptible to mechanical stress and chemical attack. cleaning does them slight damage, and they fare poorly when alcohol-containing cleaning agents are used on them. But that will soon be history. with its Degalan® vP 1034 F, evonik has developed a methacrylate resin that, when used as a binder, im-parts to plastic coatings exactly those properties that have so far been considered irreconcilable: a high-gloss surface combined with good resistance to cleaning agents. the substances responsible for these desirable properties are specialty monomers. the binder was developed mainly for the high-end market, in other words, for the high-quality plastic coatings used for cell phones, designer stereo systems, and flat-screen tvs. the binder can be used in either a single-coat or two-coat process. in the single-coat process, only one coat is applied on the sub-strate, usually a less substantial plastic mix. the coating must then perform two functions: ensure bonding to the underlying plastic as well as provide aesthetic appeal. in the two-coat process, a coat based on the new binder is applied for the color and is overlaid by a clear coat based on Uv-curable or polyurethane systems for a glossy effect—as in the case of piano black. in addition to these properties, coatings containing the binder have excellent weathering resistance. Moreover, the product can also be used in metalization processes, which make it possible to produce metallic reflective coatings. it is also suitable for gravure inks such as those used for printing on packaging films.

Consumers want electronic gadgets like cell phones and flat-screen TVs not only to function reliably, but also look good. A new methacrylate resin from Evonik now makes it possible for glossy plastic coatings to withstand cleaning agents


+++ Thirty years of VESTOPLAST®

veStoPlaSt® is celebrating its birthday. For 30 years, this prod-uct family from evonik‘s coatings & additives Business Unit has been lending hot-melt adhesives their reliable bonding strength. the range of applications is broad—as an adhesive in diapers and an additive in road marking materials, and for use under carpeting or in furniture construction, to name only a few. the substances for which the veStoPlaSt® brand name stands are co- and terpolymers of ethylene, propylene, and 1-bu-tene. in combination with synthetic resins, these polyolefins have excellent adhesive power. when combined with waxes, they also lower melt viscosity and enhance the water vapor barrier effect. this versatility is important because adhesives today must be cap-able of far more than creating a durable bond between two sub-strates. “the main areas of application for our various grades of veStoPlaSt® are currently thermoplastic hot-melt adhesives for diapers, the wood and furniture industries, and the paper and packaging sector,” says Dr. lutz Mindach, head of marketing and technical service for adhesive resins. “But the product‘s environ-mental compatibility is increasingly extending its use in automo-tive interiors and in carpet applications.” capacities have been systematically expanded over the last few years to meet growing

The adhesive tester is used to determine open time and setting time for adhesives under constant conditions. Both are important parameters for adhesives

global demand. “in the growth region of asia in particular, we can point to very healthy growth rates, even in the current global econ omic downturn,” remarks Mindach. Since 1981, the product has also found application in road con-struction. asphalt treated with veStoPlaSt®, for example, can absorb higher initial stresses and disperse them more rapidly. as a result, road surfaces remain in good condition, even in sweltering heat or freezing cold. the product is used in road markings, col-ored sealing compounds, drainage openings, and bitumen sealing sheets, too. another important plus point for these environment-ally friendly polyolefins is their 100 percent recyclability.

From by-product to commercial successoriginally, the products that are so successful today were no more than by-products in general polyolefin production. their spectac-ular rise began in the 1970s, when it became possible to improve the quality of the thermoplastic polymer significantly and market research predicted increasing demand. the greatly superior prop-erties of veStoPlaSt® based hot-melt adhesives, compared to the polymers used until now, led to this completely new applica-tion area. Following its successful development, the company began, in 1981, exclusive production in what used to be the polybutene plant. capacity was gradually increased from the initial 12,000 metric tons to the present 70,000 metric tons, with expansion of the single production line to four. today, the product group com-prises about 16 different grades for a wide variety of application areas. “For the future, we want to expand into new fields of ap-plication—with functionalized types, for example—so that we’ll be far less at the mercy of economic fluctuations in individual branches of industry,” says Mindach.

+++ Evonik acquires Eli Lilly‘s U.S. Tippecanoe manufacturing site

evonik industries has acquired indianapolis, indiana-based eli lilly and company’s tippecanoe laboratories manufacturing facility in lafayette, indiana. the site, which employs about 700, manu-factures active pharmaceutical ingredients (aPi) and precursor materials for the pharmaceutical industry. the tippecanoe plant will be fully integrated into evonik’s global production and market-ing network. “the acquisition of tippecanoe laboratories enables us to meet the growing demand for intermediates and active pharma-ceutical ingredients in the pharmaceutical industry and sub stan-tially boosts our global exclusive synthesis business,” said Dr. klaus engel, chief executive officer (ceo) of evonik in dus tries.

“the pharmaceutical market is attractive, economically stable, and produces growth rates near the double-digit range every year.” in addition to the acquisition of the site, evonik and lilly will also enter into a multi-year supplier agreement for active pharma-ceutical ingredients and intermediates. “we look forward to working closely with lilly, a world-class pharmaceuticals compa-ny,” explained Dr. Hans Josef ritzert, the head of evonik’s ex clu-sive Synthesis & amino acids Business line. “we will be produc-ing ingredients for lilly and other pharmaceutical companies in accordance with the exacting good Manufacturing Practices (gMP) quality standards. our customers benefit from the tech-nology portfolio of evonik’s sites as well as from our expertise in


news

evonik industries and taipei, taiwan-based cristal Material cor-po ration have formed a new joint venture to manufacture high-quality glass lenses for next-generation leDs, which will mar-keted under the Savosil™ brand. the evonik cristal Materials corporation joint venture will complement evonik‘s strategy as a solution provider to the lighting industry while providing cristal Material corporation access to a highly innovative market. „the leD market will see many new areas of application open up. evonik cristal Materials corporation will help its customers develop new technologies faster, technologies such as Uv leDs to sterilize water, leDs in automobiles, and leDs for general ligh-ting,“ said Patrik wohlhauser, chairman of evonik Degussa gmbH‘s management board. „Participating in the joint venture offers evonik an attractive opportunity for forward integration along the

entire supply chain in the growing leD market,“ added wohl hau-ser. the lenses produced by the joint venture will be sold to leD manufacturers. the leD lenses will be produced using evonik‘s patented Sivara™ Sol-gel technology, which allows glass lenses of con-sistent quality to be manufactured in any desired shape. the pro-cess recently received the Frost and Sullivan european technology innovation award. compared to conventional light sources, such as incandescent lamps and energy-saving lights, leDs are much more energy ef-ficient, last longer, and offer many new design possibilities. Because of these advantages, leDs are increasingly used in many different lighting applications. For these reasons, thomas Her-mann, head of evonik‘s inorganic Materials Business Unit, sees great business opportunities, „the leD evolution is here, with market growth rates expected to exceed 20 percent. we strongly believe leD will become an everyday effective lighting solution and allow everyone to contribute to reduced energy consum p-tion.“ this growth in demand for leD is driven by the green lighting trend—in other words, lighting marketed as environ-mentally friendly. Underlying legal conditions, such as banning in-candescent light bulbs or legally requiring cars to drive with lights on during the day will also help this positive development. ershien tsai, chairman and founder of cristal Material cor-poration, shared this view. „glass produced by the Sivara™ Sol-gel technology is an ideal leD optics solution and is highly reliable,“ said tsai. it also offers the phosphorous in the lenses outstanding protection against humidity and heat during opera-tion and is thus ideal for outdoor lighting. tsai is pleased with the cooperation and the speed with which evonik formed the joint venture.

Glass lenses produced using Evonik‘s patented SiVARA™ Sol-Gel technology

+++ Joint venture established for manufacture of glass lenses for LEDs

the production of pharmaceutical intermediates.” in addition, evonik has many years of experience in following official and patent law requirements for patented intermediates and active pharmaceu-tical ingredients. “this announcement represents a positive outcome for em-ployees at the site, the lafayette community, and lilly,” said John lechleiter, Ph.D., lilly’s chairman and chief executive officer. “evonik is a well-established multinational company with a strong track record in producing high-quality products.” evonik maintains pharmaceutical facilities in europe and asia and has established a global distribution network with excellent

access to customers in the pharmaceutical industry. this has al-lowed evonik, which is the first western supplier to implement horizontal integration in exclusive synthesis, to position itself prom-i nently. evonik’s asian sites manufacture precursors and inter mediates as well as non-patented compounds at competitive costs. in addi-tion, the western european sites – and in future the tippecanoe facility – focus on refining intermediates and patented active phar-maceutical ingredients. this represents another mile stone in the consistent global implementation of the company‘s exclusive syn-thesis strategy.

Bright Prospects for white Biotechnology

a M i n o a c i D S F o r S P e c i a l t y a P P l i c a t i o n S


DR. ANDREAS kARAU

A

whether as important components of life-saving iv solutions or chiral building blocks for drugs, amino acids are indispensable. But pre-paring them in enantiomerically pure form is an art: the synthetic route is in many cases exceedingly complex and financially unfeasible; extracting them from protein hydrolysates is, following the BSe scare, no longer acceptable and in any case offers no access to non-natural amino acids. on the other hand, bacteria con-vert renewable raw materials like sugar into amino acids apparently very easily and, more-over, work under eco-friendly conditions if they get the right blueprint for doing their job. evonik is master of this art. Since the company switched just four years ago to fermen tation as the production process for specialty amino acids, the product palette has expanded to 14 amino acids today.

s essential building blocks for proteins and pepti-des, amino acids are indispensable to life. Human and animal nutrition, active ingredient synthesis for drugs, and a variety of technical applications

are inconceivable without them. Adding pure amino acids to animal feeds can drastically reduce the need for complex amino acid sources such as fish meal and soybean meal, which in turn goes a long way toward conserving natural re-sources (see elements 28). In the field of human nutrition, two main application areas exist. First, amino acids are used in clinical nutrition when patients must be fed parenterally, that is, by-passing the in-testinal tract; their complete daily amino acid requirements

are then covered by IV solutions. Second, amino acids serve as dietary supplements in, for example, baby nutrition or sports nutrition, to ensure that the body receives an ade-quate supply of the essential amino acids it needs for growth and energy generation. Furthermore, amino acids are important building blocks for pharmaceutical active ingredients. Essential drugs for treating high blood pressure, diabetes, HIV infections, and bacterial infections contain amino acids as building blocks. Amino acids are also being increasingly used in cosmetics and in technical applications, for example, as formulation aids or complexing agents as in chemical mechanical polish ing in the semiconductor production.

Downstream processing of amino acidsat Evonik’s site in Ham (France)

Bright Prospects for white Biotechnology


Above average growth rates

These diverse application fields have one factor in common: They are all linked to highly attractive markets with above average growth rates between 5 and 10 percent per year, de-pending on the application. In the area of specialty amino acids, Evonik, servicing a market of several hundred million euros, is extremely well positioned: It is among the global leaders offering the complete spectrum of amino acids for various markets and application fields. Right from the start, Evonik produced the amino acids L-lysine, L-threonine, and L-tryptophan for animal nutrition directly by fermentation. By contrast, many of the specialty

B i o t e c H n o l o g y

amino acids were initially produced by its wholly owned French subsidiary Evonik Rexim SAS by extraction from protein hydrolysates, a source providing access to 15 differ-ent amino acids. This protein source is of animal origin, however, and with the emergence of the debate on BSE and avian flu this production process, although scientifically prov en to be safe, lost favor with customers. Moreover, some amino acids such as L-methionine, L-tryptophan, and L-ornithine were not accessible by this route because they are not stable under the hydrolysis conditions of the extrac-tion or are present in the hydrolysates only in very small quantities. As a result, in 2005 and 2006 Rexim switched entirely from extraction to fermentative and biocatalytic production processes. Since that time it has continuously been expand-ing its product portfolio, which includes both naturally and non-naturally occurring amino acids as well as amino acid derivatives (fig. 1). A major advantage here is that Rexim is fully backward integrated for all important amino acids, through either biocatalytic or fermentative processes. Back-ward integration in this context means that Evonik controls the entire process chain: Fermentation and downstream pro-cessing of the crude amino acids as well as the subsequent fine purification are carried out at Evonik sites. Biocatalytic processes such as production of L-methionine by racemate resolution of D,L-methionine have now been established on an industrial scale at the Wuming site in China, where they have been running successfully for many years. For the fermentative processes, Rexim invested in 2006 in its own fermentation and downstream processing line at its affiliate Evonik Fermas s.r.o. in Slovakia. Here the amino acids are fermented and, in some cases, further pro- >>>

Figure 1Timeline for introduction of fermentative or biocatalytic production processes for various amino acids

L-MetL-AlaL-Asp

L-ThrL-SerL-PheL-ArgL-Lys

L-Pro

L-ValL-Ile

L-OrnL-Trp

L-Hse

2009 Time


sive rational processes. It was thus able to optimize various parameters such as productivity, yield of carbon source, and by-products in the microorganisms systematically. This con-serves resources and also reduces production costs. Figure 3 shows an example of how yields and productivities have risen over the last few years and the formation of by-prod-ucts has continuously declined.

A new path to ultrapure L-tryptophan

In addition to ongoing optimization of strains and produc-tion processes, Rexim‘s Process Research and Development also focuses on expanding the product portfolio. In 2009 alone, the company launched on the market three new fer-mentatively produced amino acids: L-tryptophan, L-homo-serine, and L-ornithine. L-Tryptophan acts as a natural antidepressant; the amino acid is a precursor of neurotransmitters in the human brain that are responsible for a feeling of well-being. It is also an important building block for derivatives used in, for exam-ple, animal cell cultures for antibody production. In all these applications, purity is key. For Rexim‘s scientists, the challenge lay in developing a highly efficient downstream processing process for obtain-ing from the crude product high-purity L-tryptophan with-out undesired impurities. They solved the problem by means of a special crystallization process that allowed the purity re-quirements of various pharmacopoeias to be not only met but significantly exceeded.

cessed to the crude crystallization stage; final downstream processing takes place in Ham, France, or Wuming, China, both of which are Rexim sites. Rexim can thus ensure GMP compliant production over the entire production chain and a high standard of quality for customers, which is required particularly by the regulated pharmaceutical markets.

Interdisciplinary collaboration as an important precondition for success

If the amino acids are used in active ingredient synthesis, strict requirements on the purity of the products and the re-producibility of the manufacturing process must be satisfied. An important prerequisite here is effective downstream processing of the amino acid which ensures high purities simultaneously with high yields. The downstream process-ing efforts depend directly on the efficiencies of the bac terial strain and fermentation process. In the past, strain development, fermentation, and down-stream processing were often developed sequentially. Today, Evonik‘s technicians work concurrently on these prob-lems in interdisciplinary teams (fig. 2). In this way, find ings from downstream processing trials on critical by-prod ucts can be integrated directly into strain and process develop-ment. This reduces development costs and time to market. While many companies have optimized their strains ini-tially by classical random mutagenesis, Rexim, in collabora-tion with the biotechnologists of Evonik‘s Bioproducts Business Line, has choosen from the start for more progres-

Figure 2Interdisciplinary collaboration in strain development, fermentation, and downstream processing saves time and money

Figure 3Effect of strain optimization on performance

Performance of original strain Performance of improved strain

Biomass

Product

Yield

Byproduct/product ratio

Other amino acids/product ratio

Strain performance Fermentation performance

Downstream processing performance

s s

Percent0 20 40 60 80 100 120 140

B i o t e c H n o l o g y


possibility. Fermentation also has the advantage that the L-homoserine so obtained can be produced from renewable raw materials and therefore be classified as a natural product. Working in conjunction with biotechnologists from Evonik‘s Bioproducts Business Line, Rexim succeeded in less than 18 months in transforming a threonine producer into a highly active homoserine producer, notably by sup-pressing the breakdown of L-homoserine to L-threonine in the cell. Employees at the Ham site have extensive chroma-tographic expertise, dating from the period when amino acids were still being obtained by extraction from protein hydrolysates. They were therefore in a good position to esta-blish a highly efficient recovery process to provide

First industrial-scale fermentative production of L-homoserine

L-Homoserine, a non-proteinogenic amino acid, is an im-portant synthetic building block for various product groups (Fig. 4). It has so far been possible to produce L-homoserine in industrial quantities only by following complex chemical synthetic routes using, for example, L-methionine as the starting material. Rexim‘s goal was therefore to develop a process allowing it to supply the market with large quanti-ties of the amino acid. Because L-homoserine is an inter-mediate in the biosynthesis of threonine (Fig. 5, p. 30), the development of a fermentation process was an obvious >>>

The fermentation building of Fermas, Evonik’s Slovakian subsidiary, in Slovenska L´upc̆a

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Protected L-homoserine derivatives

(S)-3-AminopyrrolidineBuilding block for Telcagepant

(Migraine drug)

Azetidine carboxylicacid derivatives

(S)-3-Aminotetra-hydrothiophene

(S)-3-Aminotetra-hydrofuran L-Homoserine

L-Aspartic acid semialdehyde derivatives

(S)-α-Aminobutyrolactone

Figure 4Important molecules that have L-homoserine as starting material


cost efficiently to market requirements. That this prodigious achievement—the transformation was effected in just two-and-a-half years—has paid off is evident from the significant-ly expanded product portfolio: Evonik now covers the entire spectrum of amino acids for specialty applications, and (in contrast to extraction of protein hydrolysates, which always involves coproduction) can flexibly adjust production capac-ities for individual amino acids according to demand. l

high-purity L-homoserine in high yield. The process has al-ready been transferred to the multi-ton industrial scale. This makes Evonik the first company in the world to offer on the market large quantities of fermentatively produced L-homo-serine of very high purity.

L-Ornithine directly from sugar

L-Ornithine is a proteinogenic amino acid that plays an im-portant role in the human body’s nitrogen metabolism. The amino acid and its salts are therefore used for patients with impaired liver function to stabilize liver function. The clas-sical process for producing L-ornithine is by chemical or en-zymatic conversion of L-arginine. In a project carried out with the Science-to-Business Center Bio of Creavis Technologies & Innovation Evonik‘s techni cians wanted to replace this process by a fermentative process that would allow L-ornithine to be pro duced directly from sugar. They achieved this goal by using molecular biological processes to analyze a parent strain obtained by classical mutagenesis, and then removing bottlenecks. In this way they were able to more than double the efficiency of the bacteria. Industrial production of L-ornithine started at Fermas last year. Barely four years ago Evonik achieved a complete trans-formation in production technology for specialty amino acids, moving from an extraction process to fermentation, which is more accepted in the customer industries. This established a sustainable base allowing the company to react rapidly and

DR. ANDREAS kARAUBorn 1967andreas karau is responsible for process research, development, and quality assurance for the Product-line rexim and currently located at evonik rexim SaS, an evonik affiliate in Ham, France. He studied process engineer ing at rwtH aachen, and in 1997 obtained a doctor ate from the institute for enzyme technology of the Heinrich Heine University Düssel-dorf, where he worked in the research group of Prof. Maria regina kula. He then joined evonik, where he occupied a variety of posts. in the Biotech-

nology Project House, he was responsible for establishing the test center and transferring processes from the laboratory to the pilot scale. in early 2004 he moved to the ProFerm Project House, which he headed from the end of 2005 to its successful wind-up a year later. Following a position as senior project manager in evonik‘s Bio Science-to-Business center in Marl, he took up his current post at the start of 2008.+33 323 81-4762, [email protected]

Figure 5L-Homoserine is an important intermediate in the biosynthesis of L-threonine

Sugar

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L-Methionine L-ThreonineL-Homoserine

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news

+++ Evonik at Auto Expo India

evonik industries exhibited at this year’s auto expo india in new Delhi. the chemicals Business area of evonik and its automotive industry team exhibited in the german Pavilion at india’s major automotive trade show. extending across some 140,000 square meters of space, the trade show hosted 2,100 companies from more than 25 countries, who showcased their products to some 1.8 million visitors. the theme of this year’s auto expo india “Mobility for all with focus on green technologies.” india is a heavyweight on the automobile market: it is the fourth-largest commercial vehicle market and the eleventh- largest automobile market in the world. what is more, except for china, india is the industry’s only booming automobile market, with growth at 3 percent. in this connection, exports will play an increasingly crucial role. the region’s manufacturers have acted with this trend in mind, tripling their passenger car exports from 2002 to 2007, quintuple truck export. evonik was present for the first time, along with 30 other germany suppliers, in the german Pavilion. the focus here was on fuel savings, thus echoing the theme of the event. accordingly, evonik’s automobile expertise was met enthusiastically. For ex-ample, the company’s innovative fillers for low rolling resistance tires were presented; they make it possible for motorists to save up to 8 percent in fuel consumption. Fuel lines made of evonik’s special plastics are, by virtue of their durable properties, thinner and lighter and thus more easily formable than common systems of metal or elastomers. they also lower weight considerably. also

drawing numerous visitors were interior and exterior parts made of plastic. on the outside of a car, they feature excellent Uv resist-ance and weatherability. they also lower fuel consumption and thus co2 emissions. “the german exhibit isn’t showing any signs of crisis,” com-mented Sven augustin, technical Marketing and innovation Ma n-a ger at evonik’s automotive industry team. “on the contrary: the country’s pavilion at auto expo india has grown by 40 per-cent compared to 2008, and over 2,000 exhibitors presented component parts. germany and china even had their own halls.” augustin said that german suppliers had excellent exhibits and vis ited with very high interest for local manufacturer. as regards green technology, local manufacturers like tata displayed fully electrified vehicles for the first time. “indian automobile manufac-turers are one leap ahead in performance and design and will be-gin selling their new models immediately. they are open to co-operation with german companies. often, our indian customers even have their headquarters in europe,” confirms ashok Bandella, technical market manager at evonik Degussa india. the automotive sector is evonik’s second-largest market and generates annual sales of around €2 billion (2008). the company supplies a wide range of products for the sector—from specialty chemicals for the manufacture of fuel-saving tires, high-perfor-mance plastics for fuel and coolant lines, oil additives, and plastics components for automotive interiors to lightweight bodywork and scratch-resistant high-gloss coatings.

+++ More than 300 VESTAMID® offshore lines in three years

Since its approval in mid-2006, veStaMiD® lX9020, a polyamide 12 mold-ing compound made by evonik industries, has been used in the manufacture of more than 300 non-bonded flexible pipes in the oil industry. oil com-panies are already using the pipes in offshore projects. the molding compound was tested over a two-and-a-half year period between 2003 and 2006. these studies confirmed its advantageous proper-ties over other polyamides used as barrier layers in flexible piping, properties that are crucial to the compound’s success. in collaboration with wellstream international limited, evonik has conducted intensive tests to demonstrate compliance with the international standards aPi 17J (for flexible pipes) and iSo 13628-2. the tests evaluated creep performance, ductility, thermal ex-pansion, methanol compatibility, and hydrolysis resistance as plus points. on the basis of these results, lloyd’s register granted wellstream approval in June 2006 for the use of the polyamide 12 molding compound veStaMiD® lX9020 in the manufacture of flexible pipes for conveying production and in-jection fluids in offshore crude oil production, giving the company the award of the certificate of Material Qualification for the Use of Polyamide 12 grade veStaMiD® lX9020 in non-Bonded Flexible Pipes. Since then, the molding compound has been used commercially for the manufacture of flexible pipes. the polyamide 12 grade specially developed for the purpose combines the above technical advantages with consistent product quality; this ensures outstanding processability, thereby reducing set up times, scrap, and the risk of extrusion faults.

Developed specifically for offshore applications: the new Polyamide 12 grade VESTAMID® Lx9020

Credits

PublisherEvonik Degussa GmbHInnovation Management Chemicals & CreavisRellinghauser Straße 1–1145128 EssenGermany

Scientific Advisory BoardDr. Norbert FinkeEvonik Degussa GmbHInnovation Management Chemicals & [email protected]

EditorsDr. Karin Assmann (responsible)Evonik Services GmbHEditorial [email protected]

Contributing EditorsKlaus JoppDr. Angelika Fallert-MüllerMichael Vogel

DesignMichael Stahl, Munich (Germany)

PhotosEvonik IndustriesKarsten BootmannDieter DeboMarkus SchmidtStefan WildhirtFotodesign Lichtblick/A. Langosch (p.13) Daskleineatelier/Fotolia (p.16)Justin Horrocks/iStockphoto (p.18)Stormarn/Fotolia (p.31)

Printed byLaupenmühlen Druck GmbH & Co.KGBochum (Germany)

Reproduction only with permission of the editorial office

Evonik Industries is a worldwide manufacturer of PMMA products sold under the PLEXIGLAS® trademark on the European, Asian, African, and Australian continents and under the ACRYLITE® trademark in the Americas

Evonik Industries AGRellinghauser Straße 1–1145128 EssenGermany

www.evonik.com

16.12.–21.12.2007International Symposium on Catalysis & Fine Chemicalssingapur

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events

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02/23–02/24/201010th colloquium: Joint research on adhesive technologyfrankfurt/main (germany)events.dechema.de

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04/07–04/10/2010PolycHar 18 – world Forum for advanced Materialssiegen (germany)http://polychar18.uni-siegen.de

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