Fluorinated oxyvinyl compounds

Abstract

Vinyl ether compounds having the formula: R—O—X—O—CH═CH 2 wherein R is a radical selected from R 1 —C n H m —C(═O)—, R 1 —C n H m —CH[—O—X—O—CH═CH 2 —], R 1 —C n H m —CH['O—X—O—CH═CH 2 —]C(═O)—, R 1 —C n H m —CH[—C(═O)—O—X—O—CH═CH 2 —], R 1 —C n H m —CH[—C(═O)—O—X—O—CH═CH 2 —]C(═O)—, R 1 —[CFCl—CF 2 —] p CH 2 — and HCFCl—CF 2 —, wherein R 1 is an unsubstituted or substituted fluorinated aliphatic radical, an unsubstituted or substituted fluorinated cyclic aliphatic radical, an unsubstituted or substituted fluorinated aromatic radical, an unsubstituted or substituted fluorinated araliphatic radical, or an unsubstituted or substituted fluorinated heterocyclic radical; n is an integer between 1 and 6, inclusive; n≦m≦2n; p is an integer between 1 and 20, inclusive and X is an unsubstituted or substituted aliphatic radical, an unsubstituted or substituted cyclic aliphatic radical, an unsubstituted or substituted aromatic radical, an unsubstituted or substituted araliphatic radical, or an unsubstituted or substituted heterocyclic radical; provided that when R 1 of R 1 —C n H m — is an otherwise unsubstituted fluorinated aliphatic group, X is not ethylene or propylene. Curable compositions containing the vinyl ether compounds are also disclosed, as well as polymers polymerized from the vinyl ether compounds.

What is claimed is:  
     
         1 . A process for producing an optical device comprising the steps of: 
 (a) applying a layer of a photocurable composition onto a substrate, said photocurable composition comprising between about 0.01% and about 10% by weight of at least one compound having the formula:    R—O—X—O—CH═CH 2      wherein R is a radical having the formula R 1 —CFH—CF 2 — or R 1 —CF═CF—, wherein R 1  is selected from the group consisting of unsubstituted and substituted aliphatic radicals, unsubstituted and substituted cyclic aliphatic radicals, unsubstituted and substituted aromatic radicals, unsubstituted and substituted araliphatic radicals, and unsubstituted and substituted heterocyclic radicals; and X is selected from the group consisting of unsubstituted and substituted aliphatic radicals, unsubstituted and substituted cyclic aliphatic radicals, unsubstituted and substituted aromatic radicals, unsubstituted and substituted araliphatic radicals and unsubstituted and substituted heterocyclic radicals;    (b) imagewise exposing the photocurable composition to actinic radiation to form exposed and non-exposed areas on the substrate; and    (c) removing the imagewise non-exposed areas while leaving the imagewise exposed areas on the substrate.    
     
     
         2 . The process of  claim 1 , wherein the image non-exposed areas are removed with a solvent developer.  
     
     
         3 . The process of  claim 1 , wherein said curable component is present in an amount between about 0.10% and about 2.00% by weight.  
     
     
         4 . The process of  claim 1 , further comprising a cationic photoinitiator compound.  
     
     
         5 . The process of  claim 1 , further comprising one more additives selected from the group consisting of antioxidants, photostabiliziers, volume expanders, fillers, dyes, free radical scavengers, contrast enhancers, UV absorbers and initiator compounds,  
     
     
         6 . The process of  claim 1 , wherein said initiator compound is a Lewis Acid catalyst.  
     
     
         7 . The process of  claim 1 , further comprising at least one monomer, oligomer or polymer compound having a terminal epoxide group.  
     
     
         8 . An optical device produced according to the process of  claim 1 .  
     
     
         9 . The optical device of  claim 7 , further characterized as being a waveguide, splitter, router, coupler, combiner or any combination thereof.  
     
     
         10 . The optical device of  claim 7 , wherein said substrate comprises silicon, silicon oxide, gallium arsenide, glass, polymer or a composite material.  
     
     
         11 . A polymer comprising one or more vinyl ether units having the formula:  
       
         
           
           
               
               
           
         
       
       wherein R is a radical selected from the group consisting of R 1 -C n H m —, R 1 —C n H m —C(═O)—, R 1 —C n H m —CH[—O—X—O—CH═CH 2 —, R 1 -C n H m —CH[—O—X—O—CH═CH 2 —]C(═O)—, R 1 —C n H m —CH[—C(═O)—O—X—O—CH═CH 2 —, R 1 —C n H m —CH[—C(═O)—O—X—O—CH═CH 2 —]C(═O—)—, R 1 —[CFCl—CF 2 —] p CH 2 — and HCFCl—CF 2 —; wherein RI is selected from the group consisting of unsubstituted and substituted fluorinated aliphatic radicals, unsubstituted and substituted fluorinated cyclic aliphatic radicals, unsubstituted and substituted fluorinated aromatic radicals, unsubstituted and substituted fluorinated araliphatic radicals, and unsubstituted and substituted fluorinated heterocyclic radicals; n is an integer between 1 and 6, inclusive; n.ltoreq.m.ltoreq.2n; p is an integer between 1 and 20, inclusive; and X is selected from the group consisting of unsubstituted and substituted aliphatic radicals, unsubstituted and substituted cyclic aliphatic radicals, unsubstituted and substituted aromatic radicals, unsubstituted and substituted araliphatic radicals, and unsubstituted and substituted heterocyclic radicals; provided that when R 1  of R 1 —C n H m — is an otherwise unsubstituted fluoroaliphatic radical, X is not ethylene or propylene.  
     
     
         12 . The polymer of  claim 11 , wherein R contains at least 1 chlorine or bromine.  
     
     
         13 . The polymer of  claim 11 , wherein R contains at least one radical selected from the group consisting of —OH, —COOCH 3 , —OCH 3 , —OCH 2 CH 3 , —NO 2 SH, —SCH 3 , phenyl, benzyl, cyclohexyl, cyclohexyldimethyl and chlorocylcohexyl radicals.  
     
     
         14 . The polymer of  claim 11 , wherein R 1  is selected from the group consisting of R 1 —C n H m —, R 1 —C n H m —C(═O)—, R 1 —[CFCl—CF 2 ] p CH 2 — and HCFCl—CF 2 —.  
     
     
         15 . The polymer of  claim 11 , wherein R is R 1 —C n H m —CH[—O—X—O—CH═CH 2 ]—.  
     
     
         16 . The polymer of  claim 11 , wherein R is: 
 R 1 —C n H m —CH[—O—X—O—CH═CH 2 ]—C(═O)— or R 1 —C n H m —CH[—C(═O—)—O—X—O—CH═CH 2 ]—.    
     
     
         17 . The polymer of  claim 11 , wherein R is: 
 R 1 —C n H m —CH[—C(═O)—O—X—O—CH═CH 2 ]—C(═O)—.    
     
     
         18 . The polymer of  claim 14 , wherein R 1  is a C 1 -C 12  fluorinated aliphatic radical; and X is an aliphatic, cyclic aliphatic, aromatic or araliphatic radical.  
     
     
         19 . The polymer of  claim 18 , wherein X is a 1,4-cyclohexyldimethyl radical or an alkyl radical having the formula (—CH 2 —) n , wherein n is between 2 and 4, inclusive.  
     
     
         20 . The polymer of  claim 19 , wherein R 1  is a trifluoromethyl radical.  
     
     
         21 . The polymer of  claim 11 , wherein said polymer further comprises one or more second repeating units selected from the group consisting of monomers, oligomers and polymers containing at least one terminal ethylenically unsaturated group and monomers, oligomers and polymers containing at least one terminal epoxide group.  
     
     
         22 . The polymer of  claim 11 , consisting essentially of said vinyl ether repeating units.  
     
     
         23 . An optical device comprising a substrate having light-transmissive regions coated with a polymer comprising one or more vinyl ether units having the formula:  
       
         
           
           
               
               
           
         
       
       wherein R is a radical selected from the group consisting of R 1 —C n H m —, R 1 —C n H m —C(═O)—, R 1 —C n H m —CH[—O—X—O—CH═CH 2 —], R 1 —C n H m —CH[—O—X—O—CH═CH 2 —]C(═O)—, R 1 —C n H m —CH[—C(═O)—O—X—O—CH═CH 2 —], R 1 -C n H m —CH[—C(═O)—O—X—O—CH═CH 2 —]C(═O—)—, R 1 —[CFCl—CF 2 —] p CH 2 — and HCFCl—CF 2 —, wherein R. is selected from the group consisting of unsubstituted and substituted fluorinated aliphatic radicals, unsubstituted and substituted fluorinated cyclic aliphatic radicals, unsubstituted and substituted fluorinated aromatic radicals, unsubstituted and substituted fluorinated araliphatic radicals, and unsubstituted and substituted fluorinated heterocyclic radicals; n is an integer between 1 and 6, inclusive; n.ltoreq.m.ltoreq.2n; p is an integer between 1 and 20, inclusive; and X is selected from the group consisting of unsubstituted and substituted aliphatic radicals, unsubstituted and substituted cyclic aliphatic radicals, unsubstituted and substituted aromatic radicals, unsubstituted and substituted araliphatic radicals, and unsubstituted and substituted heterocyclic radicals; provided that when RI of RI-Cnr,- is an otherwise unsubstituted fluorinated aliphatic radical, X is not ethylene or propylene.  
     
     
         24 . The optical device of  claim 23 , wherein R 1  is a C 1 —C 12  fluorinated aliphatic radical; and X is an aliphatic, cyclic aliphatic, aromatic or araliphatic radical.  
     
     
         25 . The optical device of  claim 23 , wherein said polymer comprises one or more second repeating units selected from the group consisting of monomers, oligomers and polymers having at least one terminal ethylenically unsaturated group and monomers, oligomers and polymers having at least one terminal epoxide group.  
     
     
         26 . The optical device of  claim 23 , wherein said polymer consists essentially of said vinyl ether repeating units.  
     
     
         27 . The optical device of  claim 23 , further characterized by being a waveguide, splitter, router, coupler, combiner or any combination thereof.  
     
     
         28 . An adhesive composition comprising a vinyl ether compound having the formula:  
       R—O—X—O—CH═CH 2    
       wherein R is a radical selected from the group consisting of R 1 —C n H m —, R 1 —C n H m —C(.—═O)—, R 1 —C n H m —CH[—O—X—O—CH═CH 2 —], R 1 —C n H m —CH[—O—X—O—CH═CH 2 —]C(═O)—, R 1 —C n H m —CH[—C(═O)—O—X—O—CH═CH 2 —], R 1 —C n H m —CH[—C(═O)—O—X—O—CH═CH 2 —]C(═O—)—, R 1 —[CFCl—CF 2 —] p CH 2 —, R 1 —CFH—CF 2 —, R 1 —CF═CF— and HCFCl—CF 2 —; wherein R 1  is selected from the group consisting of unsubstituted and substituted fluorinated aliphatic radicals, unsubstituted and substituted fluorinated cyclic aliphatic radicals, unsubstituted and substituted fluorinated aromatic radicals, unsubstituted and substituted fluorinated araliphatic radicals and unsubstituted and substituted fluorinated heterocyclic radicals; n is an integer between 1 and 6, inclusive; n<m<2n; p is an integer between 1 and 20, inclusive; and X is selected from the group consisting of unsubstituted and substituted aliphatic radicals, unsubstituted and substituted cyclic aliphatic radicals, unsubstituted and substituted aromatic radicals, unsubstituted and substituted araliphatic radicals, and unsubstituted and substituted heterocyclic radicals; provided that when R 1  of RI 1 —C n H m — is an otherwise unsubstituted or substituted fluorinated aliphatic radical, X is not ethylene or propylene.  
     
     
         29 . An ink composition comprising a vinyl ether compound having the formula:  
       R—O—X—O—CH═CH2  
       wherein R is a radical selected from the group consisting of R 1 —C n H m —, R 1 —C n H m —C(.—═O)—, R 1 —C n H m —CH[—O—X—O—CH═CH 2 —, R 1 —C n H m —CH[—O—X—O—CH═CH 2 —]C(═O)—, R 1 —C n H m —CH[—C(═O)—O—X—O—CH═CH 2 —], R 1 —C n H m —CH[—C(═O)—O—X—O—CH═CH 2 —]C(═O—)—, R 1 —[CFCl—CF 2 —] p CH 2 —, R 1 —CFH—CF 2 —, R 1 —CF═CF— and HCFCl—CF 2 —; wherein R 1  is selected from the group consisting of unsubstituted and substituted fluorinated aliphatic radicals, unsubstituted and substituted fluorinated cyclic aliphatic radicals, unsubstituted and substituted fluorinated aromatic radicals, unsubstituted and substituted fluorinated araliphatic radicals and unsubstituted and substituted fluorinated heterocyclic radicals; n is an integer between 1 and 6, inclusive; n<m<2n; p is an integer between 1 and 20, inclusive; and X is selected from the group consisting of unsubstituted and substituted aliphatic radicals, unsubstituted and substituted cyclic aliphatic radicals, unsubstituted and substituted aromatic radicals, unsubstituted and substituted araliphatic radicals, and unsubstituted and substituted heterocyclic radicals; provided that when R 1  of R 1 —C n H m — is an otherwise unsubstituted fluorinated aliphatic radical, X is not ethylene or propylene.  
     
     
         30 . An article comprising a film, said film comprising a polymer with one or more vinylether units having the formula:  
       
         
           
           
               
               
           
         
       
       wherein R is a radical selected from the group consisting of R 1 —C n H m —, R 1 —C n H m —C(═O)—, R 1 —C n H m —CH[—O—X—O—CH═CH 2 —], R 1 —C n H m —CH[—O—X—O—CH═CH 2 —]—C(═O)—, R 1 —C n H m —CH[—C(═O)—O—X—O—CH═CH 2 —], R 1 —C n H m —CH[—C(═O)—O—X—O—CH═CH 2 —]C(═O)—, R 1 —[CFCl—CF 2 —] p CH 2 —, R 1 —CFH—CF 2 —, R 1 —CF═CF— and HCFCl—CF 2 —, wherein R 1  is selected from the group consisting of unsubstituted and substituted fluorinated aliphatic radicals, unsubstituted and substituted fluorinated cyclic aliphatic radicals, unsubstituted and substituted fluorinated aromatic radicals, unsubstituted and substituted fluorinated araliphatic radicals, and unsubstituted and substituted fluorinated heterocyclic radicals; n is an integer between 1 and 6, inclusive; n<m<2n; p is an integer between 1 and 20, inclusive; and X is selected from the group consisting of unsubstituted and substituted aliphatic radicals, unsubstituted and substituted cyclic aliphatic radicals, un-substituted and substituted aromatic radicals, unsubstituted and substituted araliphatic radicals, and unsubstituted and substituted heterocyclic radicals; provided that when R 1  of R 1 —C n H m — is an otherwise unsubstituted fluorinated aliphatic radical, X is not ethylene or propylene.  
     
     
         31 . An article comprising a coated substrate, said substrate comprising a polymer layer, said polymer comprising one or more vinylether units having the formula:  
       
         
           
           
               
               
           
         
       
       wherein R is a radical selected from the group consisting of R 1 —C n H m —, R 1 —C n H m —C(═O)—, R 1 —C n H m —CH[—O—X—O—CH═CH 2 —]C(═O)—, R 1 —C n H m —CH[—C(═O)—O—X—O—CH 2 —]C(═O—)—, R 1 —[CFCl—CF 2 —] p CH 2 —, R 1 —CFH—CF 2 —, R 1 —CF═CF— and HCFCl—CF 2 —, wherein R 1  is selected from the group consisting of unsubstituted and substituted fluorinated aliphatic radicals, unsubstituted and substituted fluorinated cyclic aliphatic radicals, unsubstituted and substituted fluorinated aromatic radicals, unsubstituted and substituted fluorinated araliphatic radicals, and unsubstituted and substituted fluorinated heterocyclic radicals; n is an integer between 1 and 6, inclusive; n<m<2n; p is an integer between 1 and 20, inclusive; and X is selected from the group consisting of unsubstituted and substituted aliphatic radicals, unsubstituted and substituted cyclic aliphatic radicals, un-substituted and substituted aromatic radicals, unsubstituted and substituted araliphatic radicals, and unsubstituted and substituted heterocyclic radicals; provided that when R 1  of R 1 —C n H m — is an otherwise unsubstituted fluorinated aliphatic radical, X is not ethylene or propylene.  
     
     
         32 . An article comprising a fiber, said fiber comprising a polymer with one or more vinyl repeating units having the formula:  
       
         
           
           
               
               
           
         
       
       wherein R is a radical selected from the group consisting of R 1 —C n H m —, R 1 —C n H m —C(═O)—, R 1 —C n H m —CH[—O—X—O—CH═CHsub.2—], R 1 —C n H m —CH[—O—X—O—CH═CH 2 —]—C(═O)—, R 1 —C n H m —CH[—C(═O)—O—X—O—CH═CH 2 —], R 1 C n H m —CH[—C(═O)—O—X—O—CH═CH 2 —]C(═O)—, R 1 —[CFCl—CF 2 —] p CH 2 —, R 1 —CFH—CF 2 —, R 1 —CF═CF— and HCFCl—CF 2 —, wherein R 1  is selected from the group consisting of unsubstituted and substituted fluorinated aliphatic radicals, unsubstituted and substituted fluorinated cyclic aliphatic radicals, unsubstituted and substituted fluorinated aromatic radicals, unsubstituted and substituted fluorinated araliphatic radicals, and unsubstituted and substituted fluorinated heterocyclic radicals; n is an integer between 1 and 6, inclusive; n<m<2n; p is an integer between 1 and 20, inclusive; and X is selected from the group consisting of unsubstituted and substituted aliphatic radicals, unsubstituted and substituted cyclic aliphatic radicals, un-substituted and substituted aromatic radicals, unsubstituted and substituted araliphatic radicals, and unsubstituted and substituted heterocyclic radicals; provided that when R 1  of R 1 —C n H m — is an otherwise unsubstituted aliphatic radical, X is not ethylene or propylene.