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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
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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