Water-Soluble and Clickable Segmented Hyperbranched Polymers for Multifunctionalization and Novel Architecture Construction

Abstract

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.

Long‐Chain Hyperbranched Polymers: Synthesis, Properties, and Applications

“…successfully prepared regular poly(tertiarl amino methacrylate) LCHBPs of uniform linear subchains hung with tertiary amino group. The principle was stepwise radical polymerization by controlling the similar reactivity between inimer and monomer and that the polymerization rate of monomer to inimer was close to the initial feed ratio, therefore confirming the regular LCHBP structures . Such a radical initiating step growth mechanism was also shared by the well‐known ATRP method .…”

Amphiphilic Hyperbranched Polymers: Synthesis and Host‐Guest Supermolecular Coloring Application

“…The fi ltrate was concentrated by rotary evaporation and dried in a vacuum at 30 °C for 24 h. A yellow powder was recrystallized from hexane, affording 47.36 g of solid in a yield of 54.2%. FTIR (KBr): ν = 1725 cm −1 ( ν s (C = O)); 1 H NMR (300 MHz, CDCl 3 ): δ = 0.99 (t, (CH 2 ) 10 …”

“…[ 10 ] Typically, DDMAT (1.00 g, 2.7 × 10 −3 mol) and 10 mL of dichloromethane (DCM) were added to a 25 mL round-bottom fl ask. The mixture was cooled down to 0 °C, then the excess thionyl chloride (0.29 mL, 59.0 × 10 −3 mol) was added.…”

“…[ 10 ] Typically, 1-dodecanethiol (48.76 g, 0.24 mol), acetone (116.16 g, 2.00 mol), and tricaprylylmethylammonium chloride (3.91 g, 9.64 × 10 −3 mol) were added to a 500 mL round bottom fl ask. The mixture was cooled down to 10 °C under stirring, then NaOH solution (50 wt%) (20.25 g, 0.42 mol) was dropped slowly into the mixture.…”

Synthesis and characterization of branched phenylethynyl-terminated polyimides

“…However, to further extend the application of polyimides as in high-performance advanced polymeric composites, it is anxiously fabricating new kinds of PETIs with much better processability. Recently, dendrimers and hyperbranched polymers have been attracting significant attention, owing to their relatively low viscosity and excellent solubility in organic solvents [23][24][25][26][27]. However, it is well known that many hyperbranched polymers exhibit poor mechanical properties.…”