US 12,291,596 B2
Radical cascade-enabled synthesis of precision polymers with complex main-chain structures
Jia Niu, Lexington, MA (US); Hanchu Huang, Newton, MA (US); and Wenqi Wang, Brighton, MA (US)
Assigned to The Trustees of Boston College, Chesnut Hill, MA (US)
Filed by The Trustees of Boston College, Chestnut Hill, MA (US)
Filed on Oct. 27, 2021, as Appl. No. 17/512,055.
Application 17/512,055 is a continuation in part of application No. 16/701,031, filed on Dec. 2, 2019, granted, now 11,186,678.
Claims priority of provisional application 63/183,310, filed on May 3, 2021.
Claims priority of provisional application 62/773,265, filed on Nov. 30, 2018.
Prior Publication US 2022/0056200 A1, Feb. 24, 2022
Int. Cl. C08G 61/12 (2006.01)
CPC C08G 61/12 (2013.01) [C08G 2261/11 (2013.01); C08G 2261/122 (2013.01); C08G 2261/126 (2013.01); C08G 2261/164 (2013.01); C08G 2261/418 (2013.01)] 20 Claims
 
1. A method of preparing a polymer, the method comprising:
providing a compound of Formula I

OG Complex Work Unit Chemistry
 Formula I
wherein R1 is diyl group selected from —(C1-C16 alkanediyl)-O—(C═O)—R20—(C═O)—O—(C1-C6 alkanediyl), —O—(C1-C16 alkanediyl)-O—, —O—(C1-C16 alkanediyl)-(C3-C12 cyclic alkanediyl)-(C1-C16 alkanediyl)-O—, —O—(C1-C16 alkanediyl)-(C3-C12 heterocyclic alkanediyl)-(C1-C16 alkanediyl)-O—, —O—(C1-C16 alkanediyl)-(arylene)-(C1-C16 alkanediyl)-O—, —NH—(C1-C16 alkanediyl)-NH—, —NH—(C1-C16 alkanediyl)-(C3-C12 cyclic alkanediyl)-(C1-C16 alkanediyl)-NH—, —NH—(C1-C16 alkanediyl)-(C3-C12 heterocyclic alkanediyl)-(C1-C16 alkanediyl)-NH—, and —NH—(C1-C16 alkanediyl)-(arylene)-(C1-C16 alkanediyl)-NH—;
wherein R2 is an aryl group substituted with 1, 2, or 3 electron-withdrawing groups;
wherein R3 is selected from hydrogen, (C1-C16) alkyl, aryl, and heteroaryl;
wherein R20 is selected from arylene, a (C1-C12) alkanediyl, and —R21—(C1-C16 alkanediyl)-R22—; and
wherein each of R21 and R22 are independently an arylene; and
reacting the compound of Formula I in the presence of a photocatalyst and a chain transfer agent of Formula II or Formula III:

OG Complex Work Unit Chemistry
wherein R10 is selected from a group having a structure represented by a formula:

OG Complex Work Unit Chemistry
wherein n is integer having a value of 1, 2, 3, 4, 5, or 6; and,
wherein R11 is a group selected from phenyl and a C2-C12 alkyl group.