AlliedSignal, Single-Site Catalysts Link on Boron Cocatalysts for Metallocene Polymers

AlliedSignal Inc. (Morristown, NJ) and Single-Site Catalysts, a joint venture between Catalytica, Inc. (Mountain View, CA) and Germany's Sud-Chemie Group, have agreed to jointly develop and manufacture metallocene boron cocatalysts.

Boron cocatalysts are one of two key activator technologies used with metallocene catalysts. (Methylaluminoxane, or MAO, is the other.) The alliance combines the fluorination capabilities of AlliedSignal's new FluoroSolutions business with Single-Site's experience in developing and marketing organometallic catalysts and cocatalysts.

Under the agreement, FluoroSolutions will manufacture the cocatalysts from raw materials through finished products, says company director Ian Shankland.

Single-Site Catalysts was founded in November 1998 to develop metallocene single-site catalysts for olefin polymerization. While some metallocene catalysts are standard products, many producers want customized systems. Single-Site entered the cocatalyst business when it found its metallocene customers preferred to buy catalyst and cocatalyst as a single package.

Boron cocatalysts typically contain fluorinated aromatic groups. The most common boron cocatalyst, trispentafluoroborane, starts with boron fluoride and petafluorobenzene derivatives. AlliedSignal is already a major producer of boron fluoride, which is used as a Lewis acid catalyst. The company has the ability to fluorinate benzene using halogen exchange (halex), Balz Scheimann, or other reactions.

Single-Site Solutions manufactured metallocene catalysts and cocatalysts at sister company Catalytica Pharmaceutical's facilities.

In addition to standard tris- and tetrakispentafluorophenyl boron compounds, Single-Site and AlliedSignal plan to develop and manufacture other cocatalysts on a client-confidential basis.

The companies will compete against Albemarle Corp. (Baton Rouge, LA), which says it is the world's largest supplier of metallocene catalysts and cocatalysts, as well as the Western Hemisphere's only integrated organoboron cocatalysts supplier. Japanese and Russian firms also manufacture these products.

Albemarle's standard products include trispentafluorophenyl borane and trityl tetrakispentafluorophenyl borate. It also makes N,N-dimethylanilinium tetrakispentafluorophenyl borate and lithium tetrakispentafluorophenyl borate, and produces catalysts on a confidential basis.

Albemarle recently announced a new halex process that boosts yields by two to three times. Reactions also take place significantly faster and at lower temperatures. The company plans to make the process the heart of its new custom perfluorination service.

AlliedSignal is also a recent entrant to the custom fluorination business. It formed FluoroSolutions in June 1999. The business takes advantage of AlliedSignal's extensive fluorochemical product line and broad experience in fluorine chemistry.

According to Shankland, AlliedSignal is one of the few US companies with capacity for large-scale elemental fluorination (Air Products & Chemicals, Inc., Allentown, PA, is the other). In addition to halex and Balz Scheimann, it also carries out hydrofluorination and inorganic fluorine chemistry. The business is already producing intermediates for coatings, pharmaceuticals, and agricultural chemicals.

"Fluorination," says Shankland, "is not easy to practice." Many fluorinations start with hydrofluoric acid, a highly corrosive material. FluoroSolutions controls the reactions by diluting HF in nitrogen or helium, and carefully moderating reaction temperature, pressure, and fluorine concentration.

By controlling operating conditions, FluoroSolutions is able to run some reactions in conventional steel vessels, says Shankland. Others require stainless steel, Inconel, or Monel reactors. Still others demand more exotic alloys whose use Shankland regards as proprietary.

AlliedSignal has also developed the Accufluor family of electrophilic fluorinating agents. They are not catalysts, but rather chemicals designed to selectively introduce fluorine into pharmaceutical precursors towards the end of a chemical process.

While Single-Site will hand off boron fluorination to AlliedSignal, it plans to continue producing metallocenes at its own facilities. It claims experience with a broad range of ligands: substituted and unsubstituted cyclopentadienyl, indenyls and fluoenyls; nitrogen-based; and bridged (ethyl, dialkyl, silyl). It also has demonstrated the ability to make organometallic compounds with Group IV, V, and VIII metals.

For more information: Peter Kilner, General Manager, Single-Site Catalysts, 430 Ferguson Dr., Mountain View, CA 94043. Phone: 650-960-3000. Fax: 650-960-0127.

Or: Ian Shankland, Director, FluoroSolutions, Specialty Chemicals Business Unit, AlliedSignal, Inc., 101 Columbia Rd., Morristown, NJ 07962. Phone: 973-455-6922. Fax: 973-455-6394.

By Alan S. Brown