Control of polymer architectures by living ring-opening metathesis copolymerization

A method of synthesizing a graft copolymer, said method comprising 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 first reactive diluent is provided in the presence of the first macromonomer at an amount selected so as to result in formation of said graft copolymer having a first backbone incorporating said first reactive diluent and said first macromonomer in a first polymer block characterized by a preselected first graft density and/or a preselected first graft distribution of said first macromonomer;
• wherein said graft copolymer is a graft block copolymer;
• and wherein said method further comprises a step of:
• copolymerizing a second macromonomer and a second reactive diluent;
• wherein said second macromonomer comprises a second backbone precursor directly or indirectly covalently linked to a second polymer side chain group;
• thereby resulting in formation of said graft copolymer having a second backbone incorporating said second reactive diluent and said second macromonomer in a second polymer block;
• wherein said second polymer block is directly or indirectly covalently linked to said first polymer block along said backbone;
• and wherein said second polymer block has a different composition than said first polymer block;
• and wherein said second reactive diluent is provided in the presence of the second macromonomer at an amount selected so as to result in said second polymer block being characterized by a preselected second graft density and/or a preselected second graft distribution of said second macromonomer;
• wherein said first reactive diluent, said second reactive diluent, or each of said first reactive diluent and said second reactive diluent independently is defined by the formula (FX1a), (FX1b), or (FX1c):
• wherein:
• B1 is a second backbone precursor group having a strained olefin;
• each A1 is independently an anchor group having the formula (FX3a) or (FX3b):
• each L1 is independently a linker group selected from the group consisting of a single bond, —O—, C1-C10 alkyl, C2-C10 alkenylene, C3-C10 arylene, C1-C10 alkoxy, C1-C10 acyl, triazole, diazole, pyrazole, and any combination thereof;
• and each D1 is independently a dangling group that is a substituted or unsubstituted C1-C30 alkyl, C3-C30 cycloalkyl, C5-C30 aryl, C5-C30 heteroaryl, C1-C30 acyl, C1-C30 hydroxyl, C1-C30 alkoxy, C2-C30 alkenyl, C2-C30 alkynyl, C5-C30 alkylaryl, —CO2R3, —CONR4R5, —COR6, —SOR7, —OSR8, —SO2R9, —OR10, —SR11, —NR12R13, —NR14COR15, C1-C30 alkyl halide, phosphonate, phosphonic acid, silane, siloxane, silsesquioxane, C2-C30 halocarbon chain, C2-C30 perfluorocarbon, C2-C30 polyethylene glycol, a metal, or a metal complex, wherein each of R3-R15 is independently H, C5-C10 aryl or C1-C10 alkyl;
• and
• wherein said first macromonomer, said second macromonomer, or each of said first macromonomer and said second macromonomer independently is defined by the formula (FX6a), (FX6b), or (FX6c):
• where:
• B1 is said second backbone precursor group having a strained olefin;
• each A1 is independently an anchor group having the formula (FX3a) or (FX3b):
• each L1 is independently a linker group selected from the group consisting of a single bond, —O—, C1-C10 alkyl, C2-C10 alkenylene, C3-C10 arylene, C1-C10 alkoxy, C1-C10 acyl, triazole, diazole, pyrazole, and any combination thereof;
• and each P1 is independently said second polymer side chain group.