Flow controlled synthesis of bottlebrush macromolecules

A method of preparing a bottlebrush copolymer comprising:

• a) contacting a first mixture of monomers with a varying amount of an CP catalyst in a plug-flow reactor to form a macromonomer, wherein the macromonomer is covalently bonded to a ring-strained cyclic olefin, and the macromonomer is formed via a controlled polymerization (CP);
• wherein the amount of CP catalyst that contacts the first mixture is increased or decreased at the time during contact;
• b) allowing the macromonomer to grow wherein the molecular weight of the macromonomer is dependent on the amount of the CP catalyst contacting the first mixture at the time during contact while traversing the reactor, thereby forming macromonomers having different molecular weights at different points in time;
• c) feeding macromonomers from the reactor into a second mixture via a semi-batch process wherein the second mixture comprises a ROMP catalyst and a CP quenching agent, and first and second mixture form a living copolymer via grafting-through ring opening olefin metathesis polymerization (ROMP);
• and
• d) quenching the living copolymer thereby providing a bottlebrush copolymer having a bottlebrush architecture;
• wherein the molecular weight of the macromonomer continues to grow until it is quenched by the CP quenching agent, and the living copolymer has a molecular weight that continues to grow when fed the macromonomer.