End-group fidelity is the most important property for end-functional polymers. Compared to other controlled living polymerization methods, reversible addition-fragmentation chain transfer (RAFT) polymerization often yields polymers with a lower end-group fidelity, which greatly affects their applications. Herein, we report a staged-thermal-initiation RAFT polymerization for the synthesis of polymers with high thiol end-group fidelity and their high efficiencies for grafting to various gold nanoparticles (GNPs). We experimentally prove that the decrease of end-group fidelity with their molecular weight is caused by the gradual decomposition of the initiator rather than the degradation of chain-transfer agents. We show that the staged-thermal-initiation RAFT polymerization is more effective for synthesis of polymers with high thiol end-group fidelity. The grafting-to assays for various GNPs illustrate the positive correlation between the end-group fidelity of polymers and grafting-to efficiency. This work highlights the prospects for synthesis of high end-group fidelity polymers and their application in the preparation of nanoparticles-polymer hybrid materials.
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