A series of novel and narrowly polydispersed regular chain-segmented hyperbranched poly(tertiary amino methacrylate)s (HPTAM)s with hydrophilic core and hydrophobic shell were synthesized via the combination of self-condensing vinyl copolymerization (SCVCP) and reversible addition–fragmentation chain transfer (RAFT) methodology. 2-(Dimethylamino)ethyl methacrylate (DMAEMA) and 2-((2-(((dodecylthio)carbonothioyl)thio)-2-methylpropanoyl)oxy)ethyl acrylate (ACDT) at various molar feed ratios (γ, [DMAEMA]:[ACDT]) were chosen as monomers for linear segment formation of the structure. The copolymerization kinetics revealed that during the polymerization the real-time γ value kept almost constant and was consistent with the initial feed ratio. So HPTAMs possesses regular linear chains between every two neighboring branching units, which closely resemble HyperMacs in structure. Fast click-like Menschutkin reaction (i.e., quaternarization) of the segmented hyperbranched polymers with propargyl bromide and 2-azidoethyl 2-bromoacetate readily afforded water-soluble and clickable poly(propargyl quaternary ammonium methacrylate) (HPPrAM) and poly(azide quaternary ammonium methacrylate) (HPAzAM), respectively. Through Cu(I)-catalyzed azide–alkyne cycloaddition (CuAAC), the HPPrAMs were functionalized with 1-azidododecane and 2-azidoethyl 2-bromoisobutyrate, giving birth to amphiphilic hyperbranched polyelectrolytes (or hyperbranched surfactants) and hyperbranched ATRP macroinitiators, respectively. The HPAzAMs were efficiently decorated with monoalkynyl poly(ethylene glycol) (PEG-Alk) via CuAAC, generating dendritic polymer brushes, a novel architecture reported for the first time. In addition, core-functionazlied star-shaped HPPrAM-star-poly(tert-butyl acrylate) was synthesized by RAFT copolymerization and Menschutkin reaction.

A series of water soluble octa-functionalized POSSs were facilely synthesized via thiol-ene and Menschutkin click chemistry. Among them, octa-alkynyl POSS further reacted with azide-terminal alkyl long chains, resulting in a well-defined, amphiphilic octopus-like POSS. For the first time it was used for host-guest encapsulation and it exhibited an ultrahigh loading capability.

Fast and scalable production of hyperbranched polythioether-ynes was achieved by applying sequential click chemistry (SCC) via couple-monomer methodology (CMM). As a typical example, thiol-halogen click-like reaction employing strong base, KOH and thiol-yne click reaction via UV irradiation were used for precursor preparation and polymerization, respectively. Two series of hyperbranched polythioether-ynes employing two kinds of di-thiols with different reactivity have been prepared within 10 h and characterized with 1 H NMR spectroscopy and gel permeation chromatography. The hyperbranched polymers (HPs) derived from 1,6-hexanedithiol reached high weight-average molecular weight (M w ) of 230500, high weight-average degree of polymerization (DP w ) of 1224 and high degree of branching (DB) of 0.82-0.68. Postmodification of abundant alkyne terminal groups afford HPs with a greatly enhanced DB of 0.96. Heat-initiated polymerization was also attempted. The present study clearly demonstrates the robustness of application of SCC technique in the CMM strategy for fast, scalable preparation of multifunctional HPs.

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