Fluorine-Containing Polymerizable Cyclic Olefin Compound

Title Fluorine-Containing Polymerizable Cyclic Olefin Compound 

Hydrophobic fluorine-containing polymerizable cyclic olefin derivatives have been prepared that are transparent to irradiation at 160 nm or less. These monomers have excellent development characteristics and appear useful as components in a base resin of photoresist compositions. 

A reaction vessel containing l,l,l,3,3,3-hexafluoro-2-propanol (168 g) and THF (1200 g) at —70°C was treated with 1290 ml of 1.6M of butyllithium, and the temperature was gradually increased to 0°C. The mixture was stirred at this temperature for 30 minutes and then treated with of 5-norbornene-2-carboxaldehyde (134 g) and stirred for an additional 60 minutes. After quenching with dilute hydrochloric acid, the mixture was subjected to standard aqueous workup. The crude product was purified by silica gel column chromatography, and the product was isolated in 80% yield. 

A mixture consisting of the Step 1 product (288 g) and toluene (1500 g) was refluxed, and water was removed during this period. The mixture was cooled and concentrated, and the product was isolated in quantitative yield. 

TABLE 1. Selected perfluoro alcohols and corresponding Step 1 prodnct yields. 

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