## 1 Introduction
Another approach uses an azomethylmalonodinitrile-substituted styrene derivative for the preparation of highly branched polymers through a radical process [41]. These dithioester, dithiocarbamate, and malonodinitrile approaches based on reversible termination/transfer agents are all effective at avoiding crosslinking reactions, even in nonliving systems under UV radiation or thermal decomposition. [PERSON] _et al._ applied acyclic diene metathesis polymerization (ADMET) to a variety of AB\({}_{2}\) monomers under mild reaction conditions. Using imidazolinylidene-based catalysts, electron-poor olefins did not homodimerize but switched to attack the more reactive olefins to perform a secondary metathesis reaction, leading to hyperbranched poly(ester ene)s without any gelation [36]. A few studies based on the concept of \"active site transfer\" have demonstrated the distinctive benefits of directly polymerizing existing commodity monomers or catalysts. One is related to the use of a styrene derivative containing a chlorodimethylsilyl substituent that undergoes quantitative Sn\({}_{2}\) reactions during anionic polymerization. This system requires slow addition of the monomer to avoid gelation [42]. The \"active site transfer\" mechanism can also be designed to yield soluble products through free radical copolymerizations of monomers and crosslinkers. [PERSON] _et al._ investigated the effect of adding large amounts of thiol-based chain transfer agents to avoid gelation to obtain branched methacrylic copolymers [43]. The specific concept of \"active site transfer\" has also been investigated in the RAFT polymerization of methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA) [44]; anionic SCVP of divinylbenzene (DVB) and 1,3-isopropylenebenzene [45]; AT-SCVP of DVB and (1-bromoethyl)benzene [46]; AT-SCVP of EGDMA and bisphenol A dimethacrylate [47]; and deactivation-enhanced AT-SCVP of commercially available multifunctional vinyl monomers [48]. A remarkable approach using Pd(II) and Ni(II) catalysts and very bulky chelating diimine ligands [49, 50, 51], has been reported for the formation of hyperbranched polyethylene at low pressure (a so-called \"chain walking\" process). The mechanism of active site transfer occurring predominantly among intra-chain provides a facile approach for controlling the topology of polyethylene. Hence, developing new synthetic routes with control over polymer topology is of great interest, as is the preparation of dendritic materials with controlled architectures. Accordingly, using commodity monomers and catalysts, we wished to combine the concept of \"active site transfer\" with AT-SCVP, by manipulatingcatalyst solubility during polymerization to synthesize hyperbranched polymers in a simple, one-pot procedure. Some literatures have illustrated one-pot procedure to control over polymer topologies with different single solvents, different thermostated temperatures or adding specific reagents [52, 53, 54, 55]. Besides, cupric complexes (_i.e._, Cu(I)/ligand or Cu(II)/ligand) have significantly different solubilities in various solvents at various temperatures [56]. To the best of our knowledge, there have been no previous reports of manipulating differences in solubility to control polymer topologies through variations in temperature or solvent in a one-pot procedure. In this paper, we report a facile and simple methodology for controlling polymer topologies. As displayed in Scheme 2I, poor solubility conditions for a cupric complex allowed atom transfer radical reactions to occur initially in the presence of an initiator with a more-active initiating site, a Cu(I) complex (_i.e._, activator), a monomer, and an inner with less-active initiating site. After initiating the more-active site through atom transfer reaction and producing a higher-oxidation-state Cu(II) complex (_i.e._, deactivator), the heterogeneity/precipitation of the deactivator leads the polymerization to a conventional free radical mechanism.