Synthesis of fluoroalcohol-substituted (meth)acrylate esters and polymers derived therefrom

Abstract

This invention relates to processes for preparing fluoroalcohol-substituted (meth)acrylate esters. This invention also relates to block copolymers incorporating repeat units derived from fluoroalcohol-substituted (meth)acrylate esters, and photoresists derived therefrom.

1 . A process for the preparation of a fluoroalcohol-substituted (meth)acrylate ester of formula CH 2 ═C(R)CO 2 CH 2 C(R f ) 2 OH, comprising reacting CH 2 ═C(R)CO 2 H with a fluorinated epoxide 3, 
       
         
           
           
               
               
           
         
       
       in the presence of a catalyst, wherein R is H or a C 1 -C 4  alkyl group, and R f  is a fluorinated C 1 -C 10  alkyl group. 
     
     
         2 . The process of  claim 1 , wherein R f  is CF 3 . 
     
     
         3 . The process of  claim 1 , wherein R is H or CH 3 . 
     
     
         4 . The process of  claim 1 , wherein the catalyst is selected from the group consisting of PPN chloride and quaternary ammonium halides. 
     
     
         5 . A block copolymer of the form A m -B n , wherein m and n are integers greater than 2;
 each A is independently selected and each A is a repeat unit derived from an acrylic monomer selected from the group consisting of CH 2 ═C(R)CO 2 CH 2 C(R f ) 2 OH and CH 2 ═CR 1 CO 2 R 2 , wherein   R is H or a C 1 -C 4  alkyl group;   R f  is a fluorinated C 1 -C 10  alkyl group;   R 1  is selected from the group consisting of H, F, C 1 -C 5  alkyl, and C 1 -C 5  fluoroalkyl;   R 2  is selected from the group consisting of C 1 -C 20  acyclic alkyl, C 5 -C 50  cyclic alkyl, and C 7 -C 50  polycyclic alkyl; and   each B is independently selected and is a repeat unit derived from an acrylic monomer selected from the group consisting of CH 2 ═C(R)CO 2 CH 2 C(R f ) 2 OH and CH 2 ═CR 3 CO 2 R 4 , wherein   R 3  is selected from the group consisting of H, F, C 1 -C 5  alkyl, and C 1 -C 5  fluoroalkyl; and   R 4  is selected from the group consisting of —C(R 5 )(R 6 )(CH 2 ) p R f , —C(R 5 )((CH 2 ) p R 7 ) 2 , —(CH 2 ) p R 7 , and —(CH 2 ) p —O—(CH 2 ) p R 7 , wherein   p is an integer from 1 to 4;   R 7  is C 2 -C 14  perfluoroalkyl; and   R 5  and R 6  are independently selected from the group consisting of H, C 1 -C 3  alkyl, or taken together form a 5- or 6-membered ring.   
     
     
         6 . A photoresist comprising:
 a. a block copolymer of the form A m -B n , wherein m and n are integers greater than 2;
 each A is independently selected and each A is a repeat unit derived from an acrylic monomer selected from the group consisting of CH 2 ═C(R)CO 2 CH 2 C(R f ) 2 OH and CH 2 ═CR 1 CO 2 R 2 , wherein 
 R is H or a C 1 -C 4  alkyl group; 
 R f  is a fluorinated C 1 -C 10  alkyl group; 
 R 1  is selected from the group consisting of H, F, C 1 -C 5  alkyl, and C 1 -C 5  fluoroalkyl; 
 R 2  is selected from the group consisting of C 1 -C 20  acyclic alkyl, C 5 -C 50  cyclic alkyl, and C 7 -C 50  polycyclic alkyl; and 
 each B is independently selected and is a repeat unit derived from styrene or an acrylic monomer selected from the group consisting of CH 2 ═C(R)CO 2 CH 2 C(R f ) 2 OH and CH 2 ═CR 3 CO 2 R 4 , wherein 
 R 3  is selected from the group consisting of H, F, C 1 -C 5  alkyl, and C 1 -C 5  fluoroalkyl; and 
 R 4  is selected from the group consisting of —C(R 5 )(R 6 )(CH 2 ) p R f , —C(R 5 )((CH 2 ) p R 7 ) 2 , —(CH 2 ) p R 7 , and —(CH 2 ) p —O—(CH 2 ) p R 7 , wherein 
 p is an integer from 1 to 4; 
 R 7  is C 2 -C 14  perfluoroalkyl; and 
 R 5  and R 6  are independently selected from the group consisting of H, C 1 -C 3  alkyl, or taken together form a 5- or 6-membered ring; and 
   b. a photoactive group.