Method of polymerizing cyclic olefins and vinyl olefins, copolymer produced by the method and political anisotropic film comprising the same

Abstract

A method of copolymerizing cyclic olefins and polar vinyl olefins, a copolymer produced by the method, and an optical anisotropic film including the copolymer are provided. According to the copolymerization method, a cyclic olefin and a polar vinyl olefin can be effectively copolymerized using a catalyst system composed of a compound containing a group 13 element and a radical initiator. The resulting copolymer is transparent, and has high adhesion, thermal stability, optical anisotropy and strength, and a low dielectric constant. The optical film including the copolymer can be used as a plastic lens, a polarizer protective film, an adhesive film, and a compensation film, and in a LCD display.

1 - 8 . (canceled) 
   
   
       9 . A copolymer produced by the method of copolymerizing cyclic olefing and polar vinyl olefins, comprising:
 contacting a cyclic olefin monomer and a polar vinyl olefin monomer with a catalyst system comprising:   i) a compound represented by formula (1) containing a group 13 element; and   ii) a radical initiator composed of an azo compound represented by formula (2) or a peroxide compound represented by formula (3):
   M(R 0 ) n1 (OR 1 ) n2 (X) n3    (1) 
   where M is a group 13 element;   O is an oxygen atom;   each of n1, n2, and n3 is independently an integer of 0-3 and n1+n2+n3=3;   each of R 0  and R 1  is independently a hydrogen atom; a linear or branched C 1-20  alkyl alkenyl, or vinyl; a C 5 - 12  cycloalkyl optionally substituted by a hydrocarbon; a C 6-40  aryl optionally substituted by a hydrocarbon; or a linear or branched C 1-20  alkyl or aryl containing 1-10 hetero atoms selected from a group consisting of N, O, and halogen atoms; and   X is a halogen atom;
   A 1 -N═N-A 2    (2) 
   where N is a nitrogen atom, and   each of A 1  and A 2  is independently a hydrogen atom; a linear or branched C 1-20  alkyl, alkoxy, alkenyl, or vinyl; a C 5-12  cycloalkyl optionally substituted by a hydrocarbon; a C 6-40  aryl optionally substituted by a hydrocarbon; or a linear or branched C 1-20  alkyl, alkoxy, alkenyl, aryl, or cycloalkylhetero containing a cyano group, a carbonyl group, a carboxylic group, an ether group, or an amide group;
   B 1 —O—O—B 2    (3) 
   where O is an oxygen atom; and   each of B 1  and B2 is independently a hydrogen atom: a linear or branched C 1-20  alkyl, alkoxy, alkenyl, or vinyl; a C 5-12  cycloalkyl optionally substituted by a hydrocarbon; a C 6-40  aryl optionally substituted by a hydrocarbon; or a linear or branched C 1-20  alky, alkoxy, alkenyl, aryl, or cycloalkylhetero containing a cyano group, a carbonyl group, a carboxylic group, an ether group, or an amide group,   wherein the cyclic olefin monomer is represented by formula (4):   
     
       
         
         
             
             
         
       
       where m is an integer of 0-4; R 2 , R 3 , R 4 , and R 5  may be a nonpolar functional group selected from a hydrogen atom, a halogen atom, a linear or branched C 1-20  alkyl, alkenyl, or vinyl, a C 5-12  cycloalkyl optionally substituted by a hydrocarbon, a C 6-40  aryl optionally substituted by a hydrocarbon, a C 7-15  aralkyl optionally substituted by a hydrocarbon, or a C 3-20  alkynyl; or a polar functional group selected from the group consisting of —(CH 2 ) n C(O)OR 6 , —(CH 2 ) n OC(O)R 6 , —(CH 2 ) n OC(O)OR 6 , —(CH 2 ) n C(O)R 6 , —CH 2 ) n OR 6 , —(CH 2 ) n —OR 6 , —(CH 2 ) n C(O)—O—C(O)R 6 , —(CH 2 ) n C(O)NH 2 , —(CH 2 ) n C(O)NHR 6 , —(CH 2 ) n C(O)N(R 6 ) 2 ), —(CH 2 ) n NH 2 , —(CH 2 ) n NHR 6 , —(CH 2 ) n OC(O)NH 2 , —(CH 2 ) n OC(O)NHR 6 , —(CH 2 ) n OC(O)N(R 6 ) 2 , —(CH 2 ) n C(O)Cl, —(CH 2 ) n SR 6 , —(CH 2 ) n SSR 6 , —(CH 2 ) n SO 2 R 6 , —(CH 2 ) n SO 2 R 6 , —(CH 2 ) n OSO 2 R 6 , —(CH 2 ) n SO 3 R 6 , —(CH 2 ) n OSO 3 R 6 , —(CH 2 ) n B(R 6 ) 2 , —(CH 2 ) n B(OR 6 ) 2 , —(CH 2 ) n B(R 6 )(OR 6 ), —(CH 2 ) n N═C═S, —(CH 2 ) n NCO, —(CH 2 ) n N(R 6 )C(=O)R 6 ), (CH) 2 ) n N(R 6 )C(=O)(OR 6 ), —(CH 2 ) n CN, —(CH 2 ) n NO 2 , —(CH 2 ) n P(R 6 ) 2 , —(CH 2 ) n P(OR 6 )( 2 , —(CH 2 ) n P(R 6 (OR 6 ), —(CH 2 ) n P(=O)(R) 6 ) 2 , —(CH 2 ) n P(=O)(OR 6 ) 2 , and —(CH 2 ) n P(=O)(R 6 )(OR 6 ); 
       R 6  is a hydrogen atom, a linear or branched C 1-20  alkyl, alkenyl, or vinyl, a C 5-12  cycloalkyl optionally substituted by a hydrocarbon, a C 6-40  aryl optionally substituted by a hydrocarbon, a C 7-15  aralkyl optionally substituted by a hydrocarbon, or a C 3-20  alkynyl; and, n is an integer of 0-10; when R 2 , R 3 , R 4 , and R 5  are a polar functional group, a hydrogen atom, or a halogen atom, R 2  and R 3 , or R 4  and R 5  can be connected to each other to form a C 1-10  alkylidene group, or R 2  or R 3  can be connected to one of R 4  and R 5  to form a saturated or unsaturated C 4-12  cyclic group or an C 6-17  aromatic ring compound. 
     
   
   
       10 . The copolymer of  claim 9 , which comprises 0. 1-99.9 mol % of a polar vinyl olefin monomer. 
   
   
       11 . The copolymer of  claim 9 , which has a weight average molecular weight (Mw) of 10,000 or greater. 
   
   
       12 . The copolymer of  claim 9 , which has a glass transition temperature (Tg) of 100° C. or greater. 
   
   
       13 . The copolymer of  claim 9 , which is a copolymer blend which further includes at least one of a cyclic olefin monomer, a polar vinyl olefin monomer, a non-polar vinyl olefin monomer, or a copolymer of a cyclic olefin monomer and a polar vinyl olefin. 
   
   
       14 . A polarizer protective film comprising the copolymer of  claim 9 . 
   
   
       15 . An adhesive film comprising the copolymer of  claim 9 . 
   
   
       16 . An optical anisotropic film comprising the copolymer of  claim 9 . 
   
   
       17 . The optical anisotropic film of  claim 16 , which has a retardation value (R th ) of 70 to 1000 nm, as defined by the following Equation 1:
   R th=Δ(   n   y   −n   z )× d    (1)   where n y  is a refractive index of an in-plane fast axis measured at 550 nm, n z  is a refractive index toward thickness direction measured at 550 nm, and d is a film thickness.   
   
   
       18 . The optical anisotropic film of  claim 16 , which is a negative C-plate type optical compensation film for liquid crystal display, satisfying a refractive index requirement of n x ≅n y >n z , in which n x  is a refractive index of an in-plane slow axis, n y  is a refractive index of an in-plane fast axis, and n z  is a refractive index in a direction through the film thickness. 
   
   
       19 . A liquid crystal display having a film comprising the copolymer of  claim 9 . 
   
   
       20 . A plastic lens comprising the copolymer of  claim 9 .