Control of polymer architectures by living ring-opening metathesis copolymerization

Abstract

In an aspect, a method of synthesizing a graft copolymer comprises the steps of: copolymerizing a first macromonomer and a first reactive diluent; wherein said first macromonomer comprises a first backbone precursor directly or indirectly covalently linked to a first polymer side chain group; wherein said reactive diluent is provided in the presence of the first macromonomer at an amount selected so as to result in formation said graft copolymer having a first backbone incorporating said diluent and said first macromonomer in a first polymer block characterized by a preselected first graft density or a preselected first graft distribution of said first macromonomer. In some embodiments of this aspect, said preselected first graft density is any value selected from the range of 0.05 to 0.75. In some methods, the composition and amount of said diluent is selected to provide both a first preselected first graft density and a first preselected first graft distribution.

1 - 115 . (canceled) 
     
     
         116 . A self-assembled polymer structure comprising:
 a plurality of graft block copolymers, each graft block copolymer independently comprising at least a first polymer block and a second polymer block;   wherein:   the first polymer block of each graft block copolymer comprises a first backbone and the second polymer block comprises a second backbone, the first backbone being directly or indirectly covalently linked to the second backbone;   the first polymer block comprises at least 10 first repeating units; each of said first repeating units comprising a first polymer backbone group and directly or indirectly covalently linked to a first polymer side chain group;   the first polymer block further comprises a first diluent group incorporated into the first backbone provided in an amount such that the first polymer block is characterized by a preselected first graft density of said first repeating units.   
     
     
         117 . The structure of  claim 116  being a polymer network. 
     
     
         118 . The structure of  claim 116  comprising polymer side chains capable of cross linking polymers. 
     
     
         119 . The structure of  claim 116 , wherein the preselected first graft density is selected from the range of 0.001 to 0.999. 
     
     
         120 . The structure of  claim 119 , wherein the second polymer block is characterized by a second graft density; and wherein the second graft density is selected from the range of greater than 0 to 1.0. 
     
     
         121 . The structure of  claim 116 , wherein the second polymer block of each graft block copolymer comprises:
 at least 10 second repeating units; each of said second repeating units comprising a second polymer backbone group and directly or indirectly covalently linked to a second polymer side chain group; and   a second diluent group incorporated into the second backbone provided in an amount such that the second polymer block is characterized by a preselected second graft density of said second repeating units; wherein:   the second polymer side chain group is different from the first polymer side chain group; and   said second diluent group is different from said first diluent group.   
     
     
         122 . The structure of  claim 121 , wherein the preselected second graft density is selected from the range of 0.001 to 0.999. 
     
     
         123 . The structure of  claim 116 , wherein the first polymer block of each graft copolymer is further characterized by a preselected first graft distribution of said first repeating units; and wherein the preselected first graft distribution is an alternating graft distribution, a blocky graft distribution, a random graft distribution, a linearly gradient graft distribution, or a non-linearly gradient graft distribution. 
     
     
         124 . The structure of  claim 121 , wherein the second polymer block of each graft copolymer is further characterized by a preselected second graft distribution of said second repeating units; and wherein the preselected second graft distribution is an alternating graft distribution, a blocky graft distribution, a random graft distribution, a linearly gradient graft distribution, or a non-linearly gradient graft distribution. 
     
     
         125 . The structure of  claim 116  being a lamellar structure, a matrix-sphere structure, a matrix-cylinder structure, or a matrix-gyroid structure. 
     
     
         126 . The structure of  claim 125  being a lamellar structure having a periodicity selected from the range of 20 nm to 400 nm. 
     
     
         127 . The structure of  claim 125  being a lamellar structure having a total thickness in a transverse direction selected from the range of 40 nm to 1400 nm. 
     
     
         128 . The structure of  claim 116  being a coating. 
     
     
         129 . The structure of  claim 116  being at least partially configured as a photonic crystal. 
     
     
         130 . The structure of  claim 129 , wherein said photonic crystal is configured to reflect at least a portion of wavelengths of the visible light spectrum, at least a portion of wavelengths of the infrared light spectrum, or at least a portion of wavelengths of the visible light spectrum and of the infrared light spectrum. 
     
     
         131 . The structure of  claim 116  being configured as: a transmissive surface coating, configured to transmit at least a portion of visible light; a partially reflective surface coating, configured to reflect at least a portion of visible light; a photonic crystal; a solid polymer electrolyte; a scaffold for growth of biological materials; scaffold for controlling nanoadditive distribution or orientation; a gradient mechanical property structure; or a combination thereof. 
     
     
         132 . The structure of  claim 116  being an annealed polymer network. 
     
     
         133 . The structure of  claim 116  being a polymer network characterized by a degree of crystallinity selected from the range of 10% to 90%. 
     
     
         134 . The structure of  claim 116 , comprising thermosensitive graft block copolymers or graft block copolymers having thermosensitive groups. 
     
     
         135 . The structure of  claim 116 , wherein a polydispersity index of each graft block copolymer is selected from the range of 1.00 to 1.30. 
     
     
         136 . The structure of  claim 116 , wherein the first polymer block of each graft copolymer is characterized by a first degree of polymerization of the first repeating units, the first degree of polymerization being selected from the range of 10 to 1000. 
     
     
         137 . The structure of  claim 121 , wherein the second polymer block of each graft copolymer is characterized by a second degree of polymerization of the second repeating units, the second degree of polymerization being selected from the range of 10 to 1000. 
     
     
         138 . The structure of  claim 116 , wherein each of the first repeating units is independently defined by the formula (FX10a), (FX10b), (FX10c), (FX11d), (FX11e), (FX11f), (FX11g), (FX11h), or (FX11i): 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       wherein:
 B 2  is the first backbone group; 
 each A 1  is independently an anchor group having the formula (FX3a) or (FX3b): 
 
       
         
           
           
               
               
           
         
         each L 1  is independently a linker group selected from the group consisting of a single bond, —O—, C 1 -C 10  alkyl, C 2 -C 10  alkenylene, C 3 -C 10  arylene, C 1 -C 10  alkoxy, C 1 -C 10  acyl, triazole, diazole, pyrazole, and any combination thereof; and 
         each P 1  is independently the first polymer side chain group. 
       
     
     
         139 . The structure of  claim 138 , wherein each of the first diluent groups is independently defined by the formula (FX11a), (FX11b), (FX11c), (FX11d), (FX11e), (FX11f), (FX11g), (FX11h), or (FX11i): 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
       wherein:
 B 2  is the first backbone group; 
 each A 1  is independently an anchor group having the formula (FX3a) or (FX3b): 
 
       
         
           
           
               
               
           
         
         each L 1  is independently a linker group selected from the group consisting of a single bond, —O—, C 1 -C 10  alkyl, C 2 -C 10  alkenylene, C 3 -C 10  arylene, C 1 -C 10  alkoxy, C 1 -C 10  acyl, triazole, diazole, pyrazole, and any combination thereof; and 
         each D 1  is independently a dangling group that is a substituted or unsubstituted C 1 -C 30  alkyl, C 3 -C 30  cycloalkyl, C 5 -C 30  aryl, C 5 -C 30  heteroaryl, C 1 -C 30  acyl, C 1 -C 30  hydroxyl, C 1 -C 30  alkoxy, C 2 -C 30  alkenyl, C 2 -C 30  alkynyl, C 5 -C 30  alkylaryl, —CO 2 R 3 , —CONR 4 R 5 , —COR 6 , —SOR 7 , —OSR 8 , —SO 2 R 9 , —OR 10 , —SR 11 , —NR 12 R 13 , —NR 14 COR 15 , C 1 -C 30  alkyl halide, phosphonate, phosphonic acid, silane, siloxane, silsesquioxane, C 2 -C 30  halocarbon chain, C 2 -C 30  perfluorocarbon, C 2 -C 30  polyethylene glycol, a metal, or a metal complex; and wherein each of R 3 -R 15  is independently H, C 5 -C 10  aryl or C 1 -C 10  alkyl.