Halogenated optical polymer composition

Abstract

The invention provides polymeric optical materials that can be cured in air and have low optical loss in both the C-band and the L-band of the telecommunications spectrum. The polymeric materials are made by the free radical polymerization of an at least difunctional thiol compound with an at least difunctional ethylenically unsaturated compound wherein at least one of the thiol compound and the ethylenically unsaturated compound is at least partially halogenated. The compositions of this invention may be used to fabricate planar optical waveguides with low loss and low birefringence.

1 . an energy curable composition comprising: 
 an at least difunctional thiol compound; and    an at least difunctional ethylenically unsaturated compound;    wherein at least one of the thiol compound and the ethylenically unsaturated compound is at least partially halogenated,    the ratio of thiol moieties to ethylenically unsaturated moieties is between about 1:2 and about 2:1, and    the thiol compound and the ethylenically unsaturated compound account for between about 35% and about 99.9% by weight of the energy curable composition.    
     
     
         2 . The energy curable composition of  claim 1  further comprising a selected amount of a free radical initiator.  
     
     
         3 . The energy curable composition of  claim 1  wherein at least one of the thiol compound and the ethylenically unsaturated compound includes a perfluorinated moiety.  
     
     
         4 . The energy curable composition of  claim 1  further comprising a C H  of less than about 55 M.  
     
     
         5 . The energy curable composition of  claim 1  further comprising a C H  of less than about 35 M.  
     
     
         6 . The energy curable composition of  claim 1  further comprising a C H  of less than about 20 M.  
     
     
         7 . The energy curable composition of  claim 1  further comprising a C H  of less than about 15 M.  
     
     
         8 . The energy curable composition of  claim 1  wherein the ratio of thiol moieties to ethylenically unsaturated moieties is between about 9:10 and about 10:9.  
     
     
         9 . The energy curable composition of  claim 1  wherein the ratio of thiol moieties to ethylenically unsaturated moieties is between about 19:20 and about 20:19.  
     
     
         10 . The energy curable composition of  claim 1  wherein at least one of the thiol compound and the ethylenically unsaturated compound is at least trifunctional.  
     
     
         11 . The energy curable composition of  claim 1  wherein the perfluorinated moiety is selected from the group consisting of: 
       —(CF 2 ) x —;—(C 6 F 4 ) x —;—(CF 3 ) 2 C—;—CF 2 O—[(CF 2 CF 2 O) m (CF 2 O) n ]—CF 2 —;—CF(CF 3 )O(CF 2 ) 4 O[CF(CF 3 )CF 2 O] p CF(CF 3 )—; and—CF 2 O—(CF 2 CF 2 O) m —CF 2 —, wherein x is an integer between 1 and about 10;    m and n designate the number of randomly distributed perfluoroethyleneoxy and perfluoromethyleneoxy backbone repeating subunits, respectively; and    p designates the number of —CF(CF 3 )CF 2 O— backbone repeating subunits.    
     
     
         12 . The energy curable composition of  claim 11  wherein the perfluorinated moiety is —CF 2 O—[(CF 2 CF 2 O) m (CF 2 O) n ]—CF 2 — and the ratio of m to n varies from about 0.5:1 to about 1.4:1.  
     
     
         13 . The energy curable composition of  claim 12  wherein the ratio of m to n is about 1:1 and the molecular weight of the ethylenically unsaturated compound is between about 2000 and about 2800.  
     
     
         14 . The energy curable composition of  claim 1  wherein the ethylenically unsaturated moieties are selected from the group consisting of acrylate, methacrylate, vinyl ether, allyl ether, alkene, thioacrylate ester, thiomethacrylate ester, vinyl thioether, allyl thioether, and maleimide.  
     
     
         15 . The energy curable composition of  claim 1  wherein the ethylenically unsaturated compound has the structure 
       (A) n -R—R f —R′-(A) n′ , 
       wherein 
 R f  is a perfluorinated moiety selected from the group consisting of: 
 —(CF 2 ) x —,—(C 6 F 4 ) x —,—(CF 3 ) 2 C—,—CF 2 O—[(CF 2 CF 2 O) m (CF 2 O) n ]—CF 2 —,—CF(CF 3 )O(CF 2 ) 4 O[CF(CF 3 )CF 2 O] p CF(CF 3 )—, and—CF 2 O—(CF 2 CF 2 O) m —CF 2 —, wherein x is an integer between 1 and about 10;    m and n designate the number of randomly distributed perfluoro-ethyleneoxy and perfluoromethyleneoxy backbone repeating subunits, respectively; and    p designates the number of —CF(CF 3 )CF 2 O— backbone repeating subunits;    
 R and R′ are divalent or trivalent connecting moieties selected individually from the group consisting of alkyl, aryl, ester, ether, amide, amine, and urethane groups;  
 A is an ethylenically unsaturated group selected from the group consisting of 
 CX 2 ═C(X)COE-,CX 2 ═C(CX 3 )COE-,CX 2 ═CX—,CX 2 ═CX-E-, andCX 2 ═CX—CH 2 -E-, wherein E=O or S;    each X is individually H, D, F, or Cl;    n is 1 if R is divalent, and 2 if R is trivalent;    and n′ is 1 if R′ is divalent and 2 if R′ is trivalent.    
 
     
     
         16 . The composition of  claim 14  wherein the connecting groups R and R′ are individually selected from the group consisting of  
       
         
           
           
               
               
           
         
       
     
     
         17 . The energy curable composition of  claim 1  wherein the at least difunctional thiol compound includes a perfluorinated moiety.  
     
     
         18 . The energy curable composition of  claim 17  wherein the at least difunctional thiol compound has the structure 
       (HS) n —R—R f —R′—(SH) n′ , 
       wherein 
 R f  is a perfluorinated moiety selected from the group consisting of: 
 —(CF 2 ) x —,—(C 6 F 4 ) x —,—(CF 3 ) 2 C—,—CF 2 O—[(CF 2 CF 2 O) m (CF 2 O) n ]—CF 2 —,—CF(CF 3 )O(CF 2 ) 4 O[CF(CF 3 )CF 2 O] p CF(CF 3 )—, and—CF 2 O—(CF 2 CF 2 O) m —CF 2 —, wherein x is an integer between 1 and about 10;    m and n designate the number of randomly distributed perfluoro-ethyleneoxy and perfluoromethyleneoxy backbone repeating subunits, respectively; and    p designates the number of —CF(CF 3 )CF 2 O— backbone repeating subunits;    R and R′ are divalent or trivalent connecting moieties selected individually from the group consisting of alkyl, aryl, ester, ether, amide, amine, and urethane groups;    n is 1 if R is divalent, and 2 if R is trivalent; and    n′ is 1 if R′ is divalent and 2 if R′ is trivalent.    
 
     
     
         19 . The energy curable composition of  claim 18  wherein the divalent or trivalent connecting moieties R and R′ are selected individually from the group consisting of  
       
         
           
           
               
               
           
         
       
     
     
         20 . A polymeric material comprising: 
 thioether moieties in a concentration of at least about 0.05 M; and    at least one perhalogenated moiety.    
     
     
         21 . The polymeric material of  claim 20  further comprising a C H  of less than about 55 M.  
     
     
         22 . The polymeric material of  claim 20  wherein the perfluorinated moiety is selected from the group consisting of 
       —(CF 2 ) x —,—(C 6 F 4 ) x —,—(CF 3 ) 2 C—,—CF 2 O—[(CF 2 CF 2 O) m (CF 2 O) n ]—CF 2 —,—CF(CF 3 )O(CF 2 ) 4 O[CF(CF 3 )CF 2 O] p CF(CF 3 )—, and—CF 2 O—(CF 2 CF 2 O) m —CF 2 —, wherein x is an integer between 1 and about 10;    m and n designate the number of randomly distributed perfluoroethyleneoxy and perfluoromethyleneoxy backbone repeating subunits, respectively; and    p designates the number of —CF(CF 3 )CF 2 O— backbone repeating subunits.    
     
     
         23 . Cancelled  
     
     
         24 . Cancelled  
     
     
         25 . Cancelled  
     
     
         26 . (Cancelled)  
     
     
         27 . Cancelled.  
     
     
         28 . Cancelled  
     
     
         29 . Cancelled  
     
     
         30 . Cancelled.  
     
     
         31 . (Cancelled)  
     
     
         32 . (Cancelled)  
     
     
         33 . (Cancelled)  
     
     
         34 . (Cancelled)