The controlled and efficient synthesis of polymers with tailored topologies is challenging but important for exploring structure/property research. Herein, we proposed a concept of macro-latent monomer to achieve the controlled growth of polymer topologies. The macro-latent monomer was installed by a dynamic furan/maleimide covalent bond at the chain terminal. One-shot reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene and the macro-latent monomer created controlled growth of polymer topologies. Low temperature such as 40 °C could not activate the macro-latent monomer and thus the polymerization created the homo-polystyrene. By contrast, high temperature of ∼110 °C activated the macro-latent monomer, and a maleimide-terminated macro-monomer was released via the retro-Diels Alder reaction. This macro-monomer immediately joined the cross polymerization with styrene and thus produced the side chains. By delicately manipulating the polymerization temperature, the predetermined placement of the macro-latent monomer-derived polymeric side-chains created controllably growing topologies, including star-, π-shaped, and density-variable grafting copolymers. This work paved a new way for creating on-demand topologies and would greatly enrich the topology synthesis.

具有量身定制的拓扑结构的聚合物的受控和有效合成是具有挑战性的，但对于探索结构/性质研究很重要。在这里，我们提出了一种大潜在单体的概念，以实现聚合物拓扑结构的受控增长。通过在链末端的动态呋喃/马来酰亚胺共价键安装大潜在单体。苯乙烯和大分子单体的一次性可逆加成-断裂链转移（RAFT）聚合可控制聚合物拓扑结构的生长。低温（例如40°C）无法活化大分子单体，因此聚合反应生成了均聚苯乙烯。相比之下，约110°C的高温激活了大分子潜在单体，而马来酰亚胺封端的大分子单体通过Diels Alder逆反应。该大分子单体立即与苯乙烯进行交联聚合，从而产生了侧链。通过精细地控制聚合温度，大潜在单体衍生的聚合物侧链的预定位置产生了可控制地增长的拓扑结构，包括星形，π形和密度可变的接枝共聚物。这项工作为创建按需拓扑提供了新方法，并将极大地丰富拓扑综合。