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THE LURE OF SINGLE SITE CATALYSTS Specialty chemical producers see profits in new poly olefin catalysts

Paige Marie Morse C&EN Houston

Single-site catalysts continue to create much excitement in the polyolefin industry. With the recent flurry of

activity at polymer producers, several smaller chemical companies have entered the fray, hoping to profit by applying their unique skills to this growing market.

These specialty chemical companies participate primarily at two levels— through extensions of their existing product lines or as custom manufactur­ers of the highly specialized catalyst ma­terials. Production of the common cocat-alyst aluminoxane by aluminum alkyl producers, for example, was a natural fit for Albemarle, Akzo Nobel, and Witco.

Other specialty chemical companies are leveraging their synthesis expertise, offering the ability to make the complex ligands and transition-metal complexes that are fundamental to the high activity and selectivity of these catalysts, which are often called metallocenes. Handling these materials—which are usually air-and water-sensitive and occasionally py-rophoric—requires specialized equip­ment and skills that many polyolefin pro­ducers do not have.

"The resin manufacturers are in the commodity business, not in the fine and specialty chemicals arena," says Ted M.

Catalytlca Inc. produces single-site catalysts Palo Alto, Calif., facility.

Pettijohn, director of catalyst R&D and technical service at Greenwich, Conn.-based Witco. "It's better to put [these catalysts] in the hands of people in those businesses."

Nevertheless, specialty producers have had to wait patiently for this poten­tially lucrative opportunity to develop (C&EN, July 6, page 11). "The impact of metallocenes and single-site catalysts in polyolefins has developed more slowly

Single-site catalyst systems have three key components

Organometallic complex-—Transition-metal complexes with various organic substituents. Many have cyclopentadi-enyl or substituted-cyclopentadienyl li­gands, and most are air- and water-sensi­tive. Many of these catalysts are based on early-transition metals, but more recent systems have begun to use mid- and late-transition metals as well.

Cocatalyst—Complexes that activate and enhance the performance of the transition-metal catalytic compounds and are often used in excess compared

with the metal. Aluminoxanes, made from a controlled reaction of aluminum alkyls with water, and fluorinated or­ganoboron compounds are common co-catalysts.

Support—Typically silica-based mate­rials to support the catalyst components. Most gas- and slurry-phase polymeriza­tion processes require such supports. The transition-metal loading on the sup­port is usually quite low—only 1 to 2% by weight—and the supported catalyst is consumed in the polymerization process.

than many thought it would," says Steven L. Rock, business manager for sil­ica catalysts at PQ Corp., Valley Forge, Pa. Battles over intellectual property rights are often cited as one of the major reasons for this delay.

In this highly competitive market, most specialty chemical companies are well aware of the intellectual property disputes and the need for strict secrecy clauses in their contracts with polyolefin

clients. However, the extra effort they must make to protect themselves is not enough to deter them from participating in this very lu­crative market.

Most single-site catalysts are composed of three dif­ferent materials—an organo­metallic complex, a cocata­lyst, and a support—that are based on very different chemistries. The use of these materials varies de­pending on whether the polymerization process is a solution process, which usually uses homogeneous catalysts and no support, or a gas or slurry process, which generally requires

in its East supported catalysts. This variety of chemis­

tries and the small quantity of catalyst needed often do not fit with the strategy of polyolefin producers.

"We are very conscious of our skill base and business focus," says Daryll G. Harrison, team leader of the new catalyst and polymer group at Nova Chemicals. "We have limited experience with small-volume manufacture."

Nova announced its presence in this field this fall, touting a new single-site catalyst system for its proprietary Ad­vanced Sclairtech process for polyethyl­ene (C&EN, Sept. 28, page 13). The com­pany has not yet begun commercial man­ufacture of its catalyst, but it plans to set up contracts with external companies. Nova has already chosen preferred sup­pliers for the organometallic and the co-catalyst components of its catalyst sys­tem, according to Harrison. Like most other companies in this field, Nova is not disclosing the names of these suppliers.

Dow Chemical and Exxon Chemical, widely viewed as the technology leaders in this field, also use outside expertise to provide components of their single-site catalyst systems. Both companies pur­chase the organometallic complex, co-

DECEMBER 7, 1998 C&EN 25

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catalyst, and support, if used, from out­side vendors and assemble the finished catalyst at their production sites.

For Exxon's polyethylene licensing joint venture with Union Carbide, Univa-tion Technologies, the decision to make the final catalyst itself was easy. "Both par­ent companies have expertise in manufac­turing catalysts for polyethylene," says Wil­liam R. Parr, Univation's catalyst business director. "Univation has the patent assets to cover the technology and the know-how to construct the final catalyst."

Phillips Petroleum recently began to make the organometallic component of its single-site catalyst at a new unit at its R&D site in Bartlesville, Okla. (C&EN, Aug. 17, page 10). It then ships the product to an outside vendor to load on a support for use in Phillips' slurry loop process. Phillips is using these systems in its Houston poly­ethylene plant and is planning to license its process and catalyst technology.

In contrast to these companies, Targor, the polypropylene joint venture between BASF and Hoechst, makes its own, and of­fers to make other companies', organome­

tallic components of single-site catalysts at its 5-metric-ton-per-year manufacturing site in Lamotte, France.

At this year's MetCon '98 conference on single-site catalysts in Houston, spon­sored by consulting firm Catalyst Group, Spring House, Pa., Horst Tappe, manag­ing director of metallocene chemicals at Targor (Mainz, Germany), highlighted the company's expertise in the area. "We consider ourselves the fine chemical sin­gle-site catalyst producer," he said, not­ing the company's experience from Hoechst's specialty chemical business.

Outsourcing the production of poly-olefin catalysts is not a new phenome­non. Several polyolefin producers and li­censors rely on other companies to make Ziegler-Natta or chromium-based cata­lysts—the commonly used systems to­day. What is different with single-site cat­alysts is the variety of new players and nontraditional manufacturers that have entered or expanded their product offer­ings in this emerging field.

"The discontinuity created by the new single-site technology makes it easi-

Several companies produce components of single-site catalysts

Akzo Nobel

Albemarle

Asahi Glass

Austin Chemical3

Boulder Scientific

Engelhard0

Catalytica Inc.

Crosfieldd

W.R. Grace

Norquay Technology

Laporte

PQ Corp.

SRI International

Targorh

Witco

Manufacturing locations

Deer Park, Texas

Baton Rouge, La.

Kanagawa, Japan

U.S., Europe, Japan

Mead, Colo.

Pasadena, Texas

East Palo Alto, Calif.

Warrington, U.K.

Worms, Germany; Curtis Bay, Md.

Chester, Pa.

Pullach, Germany; Teesside, U.K.

Kansas City, Kan.

Menlo Park, Calif.

Lamotte, France

Bergkamen, Germany

Components made

Cocatalyst (aluminoxane)

Organometallic complexes, cocatalysts (aluminoxane and organoboron), supported catalyst

Cocatalyst (organoboron)

Organometallic complexes, cocatalyst (organoboron13), supported catalyst

Organometallic complexes, cocatalyst (organoboron)

Supported catalyst

Organometallic complexes

Silica supports

Silica supports*3, supported catalysts

Organometallic complexes

Organometallic complexes*, cocatalysts (organoboron9)

Silica supports

Not specified

Organometallic complexes, cocatalysts, supported catalyst

Organometallic complexes, cocatalyst, supported catalyst

Related businesses

Aluminum alkyls

Fine chemicals, aluminum alkyls, custom synthesis

Fluorine chemistry, fine chemicals

Fine chemicals, custom synthesis

Fine chemicals

Catalyst manufacture

Fine chemicals

Silica chemistry

Silica chemistry, catalyst manufacture

Custom synthesis

Catalyst manufacture, fine chemicals

Silica chemistry

Custom synthesis

Fine chemicals

Aluminum alkyls

a Represents various small producers, b Markets Asahi Glass organoboron compounds in the U.S. c Acquired Catalyst Resources in May 1998. d Wholly owned subsidiary of ICI. e Made by Davison subsidiary, f Made by Peroxid-Chemie subsidiary, g Made by Fine Chemicals subsidiary, h Joint venture (50-50) between BASF and Hoechst.

er to enter the market than simply mov­ing into a well-established market area," explains James J. Barber, business direc­tor of organometallics and catalysts at Al­bemarle, Baton Rouge, La.

Albemarle's participation in this area is not entirely unexpected, considering its strength in aluminum alkyl production and related aluminoxane products. How­ever, Albemarle has extended its offering beyond the aluminoxane cocatalyst to cus­tom syntheses of organometallic complex­es and supported catalysts.

Albemarle also has built up supplies of raw materials for an emerging family of cocatalysts based on fluorine-substitut­ed aromatic compounds of boron. "We recognized that the supply base for fluo-roaromatics was quite narrow," Barber says, so the company filled the gap.

"This decision was based on the com­pany's belief that the supply of single-site catalysts and cocatalysts would never be a factor in the rate of their develop­ment," Barber says.

Witco has expanded on its initial posi­tion as an aluminum alkyl producer, Pet-

tijohn says. "We have used aluminoxanes as an entree to producing the metal-locenes themselves, and then producing the support­ed catalysts."

Catalytica Inc., Mountain View, Calif., is a relative newcomer to the single-site catalyst field, adding catalyst manufacture to its base in fine chemicals. Its subsid­iary, Catalytica Advanced Technologies, has worked on these systems since 1996 and last month joined forces with United Catalysts, a sub­sidiary of Germany's Sud-Chemie, to form a venture called Single Site Catalysts, specifically focused on poly­olefin catalysts.

"United Catalysts will pro­vide marketing expertise," says Peter H. Kilner, Catalyti­ca Advanced Technologies' director of business develop­ment. "They will also provide additional resources so we can grow the business much more quickly than we were prepared to do on our own."

Another group of produc­ers is made up of small fine chemicals companies—such as Austin Chemical, Boulder

26 DECEMBER 7, 1998 C&EN

Combinatorial chemistry methods reduce time, save money

With much effort being focused on the commercialization of single-site cata­lysts for polymer production, some companies are turning to methods bet­ter known for drug discovery than for catalyst development to find new cata­lysts rapidly or improve current sys­tems. By using these methods, compa­nies hope to save time and money as they quickly carve a niche for themselves in this rapidly evolv­ing catalyst area.

"Combinatorial chemistry techniques help to accelerate the pace of initial discovery and the rate at which one can optimize the catalyst system," says Howard Turner, director of catalysis at Sy-myx Technologies, Santa Clara, Calif. "It is a combination of rapid parallel syntheses and clever pri­mary and secondary screening protocols."

Symyx has built a 48-chamber polymerization reactor that al­lows a researcher to complete nearly 100 screening reactions a day. A significant fraction of Symyx's projects are focused on developing new catalysts for olefin polymerization, ac­cording to Turner, and several compa­nies are negotiating to take over the sponsorship of a two-year-old polyolefin program that it began with Hoechst but that Hoechst will not be continuing.

Another reason to use these tech­

niques is to establish an intellectual prop­erty position in this competitive arena quickly, says Thomas J. Baiga, president and chief executive officer of the start-up company Scylla Chemical, Carlsbad, Cal­if. Scylla also offers combinatorial chem­istry studies to clients and is a spin-off from Charybdus Technologies, which makes combinatorial chemistry reactors.

Several catalyst variations can be tested at one time using small-volume reactors.

No clients have been named yet, but Baiga says several contracts are pending and he has had many discussions with potential clients, most of which are tar­geting single-site catalyst development

The appeal of these techniques seems obvious—faster discovery and develop­ment cycles for new catalysts requiring less financial investment. However, in­

terpretation of the vast amounts of data generated by these experiments is a daunting task. "Setting up the infra­structure [data libraries] to do this is cer­tainly a challenging task," Turner says.

Molecular Simulations Inc. (MSI), a wholly owned subsidiary of Princeton, N.J.-based Pharmacopeia, expects that it has an advantage in this area because of its strength in computational chemistry, says John M. Newsam, chief scientific

officer at MSI. Pharmacopeia's acquisition of MSI gave the com­pany strength in both combina­torial chemistry techniques and library development of specialty chemicals that can be easily ap­plied to single-site catalysts, he says (C&EN, Feb. 9, page 9).

Several companies tell C&EN that these catalyst testing meth­ods sound interesting, but until a commercial success is identi­fied, they remain skeptical about the "real-world" utility of these rapid tests.

"Catalysts are usually very complex materials," explains Pe­ter H. Kilner, director of business

development at Catalytica Advanced Technologies, a subsidiary of Catalytica Inc., Mountain View, Calif. "Often the su-perautomated synthetic techniques that people have touted don't lend themselves to synthesizing real-world systems. How­ever, the idea of trying to accelerate the process for catalyst synthesis and testing is certainly a good idea."

Scientific, and Norquay Technology—that have specialized expertise in handling small quantities of highly reactive materi­als. For these companies, what started as a niche business of supplying researchers with unusual ligands has grown to a siz­able commercial catalyst business, with polyolefin producers eager to find alterna­tive sources for their specialized materials.

"Customers want diversity and multi­ple suppliers," says Robert W. Heldt, pres­ident of Norquay Technology, Chester, Pa. "Dow and Exxon, for example, don't want to be sourced from the same company." Norquay won't disclose its annual sales fig­ures but says business has grown 15 to 20% per year in recent years.

At Mead, Colo.-based Boulder Scientif­ic, about half of its business is the cus­tom synthesis of single-site organometal-lic complexes, and the company is plan­ning to expand its production capacity in the next 18 months. "This field still has a lot of growth left to it," President John Birmingham says.

Most of the specialty players in this field note the high growth potential for this market—predicting 15 to 25% pene­tration by single-site-made polymers into the polyolefin market by 2005—and ex­pect that their business will continue to grow quickly. However, few companies are willing to share specific numbers on the size of the catalyst opportunity or their production capacity.

Christoph Hartmann, business direc­tor of applied catalysts at Peroxid Che-mie, a subsidiary of the U.K.'s Laporte, estimates that 4 metric tons per year of organometallic complexes is currently being used in polyolefin single-site cata­lysts. This estimate fits well with the 2- to 4-metric-ton demand provided by Mari-faith Hackett, senior consultant at the market research firm SRI Consulting, Menlo Park, Calif., which is based on an estimated global consumption of about 500,000 metric tons of metallocene-made polyethylene in 1998.

Although the quantities used seem

small, single-site catalysts are very active and can produce large volumes of poly­mer. Typical Ziegler-Natta systems pro­duce about 2,000 lb of polymer per pound of supported catalyst, according to Kenneth B. Sinclair, principal at the consulting firm STA Research, Sunnyvale, Calif. At two to five times the activity, 1 lb of many supported single-site cata­lysts, which are loaded with only 1 to 2% by weight of the organometallic compo­nent, can make 4,000 to 10,000 lb of polymer.

However, Sinclair cautions that these values can vary significantly in actual pro­duction. "The overall yield depends on how the plant equipment is being used," Sinclair says, and whether the polymer producer is focused on getting the most polymer per pound of catalyst or per hour of reactor time.

Although several polyolefin compa­nies are producing polyolefins made with single-site catalysts, many catalyst producers report that these companies

DECEMBER 7, 1998 C&EN 27

b u s i n e s s fe:v;-;.

continue to optimize the performance of their catalysts, typically with an eye on cost reduction.

"Our customers [polyolefin producers that develop the catalysts] are working on getting the activity up and the cost per pound down," Catalytica's Kilner says, "while we use organic synthesis technologies to produce the compounds more cost effectively." Typical prices for the organometallic component of these systems range from $1,000 to $10,000 per kg, according to Kilner.

New catalyst supports are also being evaluated, says PQ's Rock. "We are find­ing that companies that have demonstrat­ed commercial grades [of metallocene-made polymers] are now going back to look at some of the more subtle effects of support properties to determine which properties are the best for their catalyst formulation," he says.

"The need to support metallocenes and related cocatalysts adds an extra di­mension of complexity," says Phil G. Lev-iston, plastics business unit leader at Crosfield, a wholly owned subsidiary of ICI. "There should not be an automatic

Witco's aluminoxane production site in Bergkamen, Germany.

assumption that those supports, which are proven for [other polyolefin cata­lysts], are optimum for metallocenes."

After major strides in these optimiza­tion efforts, most catalyst and polyolefin

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producers now agree that catalyst costs are no longer an issue in their develop­ment. The cost for some single-site cata­lysts has fallen to 0.4 to 0.6 cent per lb of polymer from near 2 cents per lb, ac­cording to Sinclair, compared with 0.2 cent for Ziegler-Natta systems.

However, although catalyst costs are coming down, legal costs continue to sky­rocket in this increasingly litigious field.

"I have never seen an area so land-mined with legal issues as this one," SRI's Hackett says. "Everyone who is active in the area of metallocene polyolefins is concerned about lawsuits."

As specialty companies move into the single-site catalyst market, they are quick­ly realizing that a strong legal strategy is as important as—if not more important than—a strong business strategy. Wheth­er that means including indemnity claus­es in contracts with their polyolefin cli­ents—to ensure they are not liable if patent infringement occurs—or staking a claim to their own intellectual property in the catalyst manufacturing process, it is a carefully planned approach.

Although there has been some delay in the use of single-site catalysts in the polyolefin market—for many different reasons, including intellectual property disputes—most participants continue to believe that significant market penetra­tion will occur.

"We regard the potential of these single-site catalysts as quite high," Albe­marle's Barber says. "In 10 to 15 years, the polyolefin market will look quite dif­ferent than it does today on account of these types of catalysts."^

28 DECEMBER 7, 1998 C&EN