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US 7,442,828 B2Granted
Precursors to fluoroalkanol-containing olefin monomers, and associated methods of synthesis and use
AssigneeInternational Business Machines Corporation
InventorsGregory Breyta, Richard Anthony DiPietro, Daniel Joseph Dawson
Life of this patent
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Abstract
The invention provides alkene fluoroalkanol and fluorinated polyol precursors to fluoroalkanol-substituted α,β-unsaturated esters. The fluoroalkanol-substituted α,β-unsaturated esters are olefins that can be readily polymerized to provide fluoroalkanol-substituted polymers useful in lithographic photoresist compositions. Also provided are methods for synthesizing the alkene fluoroalkanol and fluorinated polyol precursors.
Claims20
A fluoroalkanol-substituted α,β-unsaturated ester having the structure of formula (VIII)
- wherein:
- R31 and R32 are independently selected from hydrogen, C1-C24 alkyl, substituted C1-C24 alkyl, and —(CO)—R in which R is hydrogen, hydroxyl, halo, C1-C24 alkyl, substituted C1-C24 alkyl, amino, C1-C24 alkylamino, or di(C1-C24 alkyl)amino, with the proviso that at least one of R31 and R32 is fluorinated, and further wherein R31 and R32 may be taken together to form a fluorinated alicyclic group;
- R39 and R40 are independently selected from hydrogen, C1-C24 alkyl, substituted C1-C24 alkyl, and —(CO)—R in which R is hydrogen, hydroxyl, halo, C1-C24 alkyl, substituted C1-C24 alkyl, amino, C1-C24 alkylamino, or di(C1-C24 alkyl)amino, with the proviso that at least one of R39 and R40 is fluorinated and further wherein R39 and R40 may be taken together to form an alicyclic group;
- R33, R34, R35, R36, R37, and R38 are selected from hydrogen, C1-C24 alkyl, and substituted C1-C24 alkyl, and further wherein any two of R33, R34, R35, R36, R37, and R38 may be taken together to form a ring, with the proviso that one of R36 and R37 is hydrogen, and the other has the structure of formula (VI)
- wherein R17 is selected from hydrogen, fluoro, C1-C4 alkyl, fluorinated C1-C4 alkyl, —CH2—COOH, —CF2—COOH, —CH2—COOR20, and —CF2—COOR20, R18 is hydrogen or fluoro, R19 is hydrogen, fluoro, or —COOH, and R20 is a nonhydrogen substituent.
2 more elements
A fluoroalkanol-substituted α,β-unsaturated ester having the structure of formula (IX)
- wherein:
- R41, R42, R48, R49, R52, and R53 are independently selected from hydrogen, C1-C24 alkyl, substituted C1-C24 alkyl, and —(CO)—R in which R is hydrogen, hydroxyl, halo, C1-C24 alkyl, substituted C1-C24 alkyl, amino, C1-C24 alkylamino, or di(C1-C24 alkyl)amino, with the provisos that (a) at least one of R41 and R42, (b) at least one of R48 and R49, and (c) at least one of R51 and R52 is fluorinated;
- and
- R43, R44, R46, R47, R50, and R51 are independently selected from hydrogen, C1-C24 alkyl, and substituted C1-C24 alkyl, and further wherein any two of R43, R44, R46, R47, R50, and R51 may be taken together to form an alicyclic group, with the proviso that one of R45 and R46 is hydrogen, and the other has the structure of formula (VI)
- wherein R17 is selected from hydrogen, fluoro, C1-C4 alkyl, fluorinated C1-C4 alkyl, —CH2—COOH, —CF2—COOH, —CH2—COOR20, and —CF2—COOR20, R18 is hydrogen or fluoro, R19 is hydrogen, fluoro, or —COOH, and R20 is a nonhydrogen substituent.
2 more elements
A method for synthesizing a fluoroalkanol-substituted α,β-unsaturated ester, comprising:
- (a) synthesizing a fluorinated polyol having the structure of formula (IV)
- wherein
- R1 is selected from hydrogen, C1-C24 alkyl, substituted C1-C24 alkyl, C1-C24 alkoxy, and substituted C1-C24 alkoxy,
- R2, R3, R4, and R5 are independently selected from hydrogen, C1-C24 alkyl, and substituted C1-C24 alkyl, and further wherein any two of R1, R2, R3, R4, and R5 may be taken together to form a ring,
- R6A is selected from hydrogen, C1-C24 alkyl, substituted C1-C24 alkyl, and —(CO)—R in which R is hydrogen, hydroxyl, halo, C1-C24 alkyl, substituted C1-C24 alkyl, amino, C1-C24 alkylamino, or di(C1-C24 alkyl)amino,
- R7A is C1-C24 alkyl or substituted C1-C24 alkyl, with the proviso that at least one of R6A and R7A is fluorinated, and
- one of R13 and R14 is hydroxyl and the other is selected from hydrogen and hydroxyl, by admixing an alkene fluoroalkanol having the structure of formula (III)
- with a substituted or unsubstituted borane to provide a reaction mixture, and thereafter adding aqueous base and hydrogen peroxide, to the reaction mixture;
- and
- (b) contacting the fluoroalkanol with an acylation reagent selected from acyl chlorides of the formula Cl—(CO)—CR17═CR18R19 and anhydrides of the formula O[(CO)—CR17═CR18R19]2 under reaction conditions effective to result in esterification of a hydroxyl group present at R13, R14 or at both R13 and R14, to provide a —O—(CO)—CR17═CR18R19 substituent, wherein R17 is selected from hydrogen, fluoro, C1-C4 alkyl, fluorinated C1-C4 alkyl, —CH2—COOH, —CF2—COOH, —CH2—COOR20, and —CF2—COOR20, R18 is hydrogen or fluoro, R19 is hydrogen, fluoro, or —COOH, and R20 is a nonhydrogen substituent.
7 more elements
A method for synthesizing a fluoroalkanol-substituted α,β-unsaturated ester, the method comprising:
- (a) contacting (i) an olefinic reactant directly substituted on an olefinic carbon atom with a substituted or unsubstituted methyl group with (ii) a fluorinated carbonyl compound under reaction conditions and for a time period effective to allow addition of the olefinic reactant to the carbonyl carbon of the fluorinated carbonyl compound, thereby providing an alkene fluoroalkanol;
- (b) hydroxylating the alkene functionality in the alkene fluoroalkanol by subjecting the alkene fluoroalkanol to a hydroboration reaction, thereby providing a saturated fluoroalkanol containing at least one additional hydroxyl group;
- (c) acylating the additional hydroxyl group by contacting the saturated fluoroalkanol with an acylation reagent selected from acyl chlorides and anhydrides under esterification conditions.
A fluorinated polyol having the structure of formula (VIIIA)
- wherein:
- R31 and R32 are independently selected from hydrogen, C1-C24 alkyl, substituted C1-C24 alkyl, and —(CO)—R in which R is hydrogen, hydroxyl, halo, C1-C24 alkyl, substituted C1-C24 alkyl, amino, C1-C24 alkylamino, or di(C1-C24 alkyl)amino, with the proviso that at least one of R31 and R32 is fluorinated, and further wherein R31 and R32 may be taken together to form a fluorinated alicyclic group;
- R39 and R40 are independently selected from hydrogen, C1-C24 alkyl, substituted C1-C24 alkyl, and —(CO)—R in which R is hydrogen, hydroxyl, halo, C1-C24 alkyl, substituted C1-C24 alkyl, amino, C1-C24 alkylamino, or di(C1-C24 alkyl)amino, with the proviso that at least one of R39 and R40 is fluorinated and further wherein R39 and R40 may be taken together to form an alicyclic group;
- R33, R34, R35, R36, R37, and R38 are selected from hydrogen, C1-C24 alkyl, and substituted C1-C24 alkyl, and further wherein any two of R33, R34, R35, R36, R37, and R38 may be taken together to form a ring, with the proviso that one of R36 and R37 is hydrogen, and the other is hydroxyl.
1 more element
A fluorinated polyol having the structure of formula (IXA)
- wherein:
- R41, R42, R48, R49, R52, and R53 are independently selected from hydrogen, C1-C24 alkyl, substituted C1-C24 alkyl, and —(CO)—R in which R is hydrogen, hydroxyl, halo, C1-C24 alkyl, substituted C1-C24 alkyl, amino, C1-C24 alkylamino, or di(C1-C24 alkyl)amino, with the provisos that (a) at least one of R41 and R42, (b) at least one of R48 and R49, and (c) at least one of R51 and R52 is fluorinated;
- and
- R43, R44, R46A, R47, R50, and R51 are independently selected from hydrogen, C1-C24 alkyl, and substituted C1-C24 alkyl, and further wherein any two of R43, R44, R46A, R47, R50, and R51 may be taken together to form an alicyclic group, with the proviso that one of R45A and R46A is hydrogen, and the other is hydroxyl.
1 more element
Dependencies are inferred from the claim text.