Synthesis, Dye Encapsulation, and Highly Efficient Colouring Application of Amphiphilic Hyperbranched Polymers

Abstract

A novel kind of amphiphilic hyperbranched polymer (AHP), poly(2-(dimethylamino)ethyl methacrylate)-co-polystyrene (HPTAM-co-PS), was synthesized via the combination of reversible addition–fragmentation chain-transfer polymerization and self-condensing vinyl polymerization (RAFT-SCVP). HPTAM-co-PS was functionalized via the highly efficient Menschutkin click reaction, resulting in hyperbranched poly(propargyl quaternary ammonium methacrylate)-co-polystyrene (HPPrAM-co-PS) with a hydrophilic quaternary ammonium salt core and hydrophobic PS shell. The average numbers of dye molecules trapped by each molecule of HPPrAM-co-PS (24.2 kDa) were 24.1 for methyl orange (MO), 22.0 for fluorescein sodium (FS), 24.2 for rose bengal (RB), and 238.4 for Congo red (CR). The polymer–dye complexes show excellent colouring effects for both PS and poly(styrene-b-butadiene-b-styrene) (SBS) membranes; the colour of the membrane containing AHP is very stable and uniform. Our work opens an avenue for the design of efficient dye-colouring additives and for the application of hyperbranched polymers in the field of polymer colouring.

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

“…With a three-dimensional irregular structure and numerous binding sites, amphiphilic HPs (AHPs) have been explored to encapsulate dye molecules for coloring through a phase-transfer process, due to their self-assembling behavior. [ 5 ] Compared with linear copolymers, AHPs with an irregular architecture will self-assemble into a looser aggregation in solvents, which enables them to accommodate more dye molecules than linear ones. [ 3 ] Furthermore, AHPs have numerous binding sites which can interact with dyes.…”

“…[ 3,5 ] In this work, AHPs with a water soluble core and hydrophobic shell were synthesized using a SCVP-RAFT strategy to enhance the polarity difference between the core and shell (Scheme 1 ). The hydrophobic shell can effi ciently prevent the captured dyes escaping from the polymer-dye complex.…”

“…[ 5 ] For instance, 5 mL of PMMA chloroform solution (0.1 g mL −1 ) was well mixed with 0.5 mL of as-prepared chloroform solution of polymer-dye complexes. The mixture was transferred into a culture dish and covered with a fi lter paper.…”

“…Additionally, resonance signals locating at 44.9 ppm (labeled with "c") were ascribed to back- HPPrAM-co -PMMA easily. [ 5,6 ] However, the trapped dyes found it diffi cult to escape, due to both the strong interaction between the binding sites and dyes and the shielding effect of the hydrophobic PMMA shell. Hence, the dye molecules were effi ciently transferred from the water phase into the chloroform phase (as shown in Scheme 2 ).…”

Synthesis and characterization of hyperbranched amphiphilic block copolymers prepared via self‐condensing RAFT polymerization

“…These hyperbranched copolymers can be cleaved and form comb‐like copolymers. The second example concerns also the synthesis of random amphiphilic hyperbranched copolymers of 2‐(dimethylamino)ethyl methacrylate and styrene, synthesized for the encapsulation of dyes, using ((dodecylsulfanylthiocarbonylsulfanyl)‐2‐methylpropanoyloxy)ethyl acrylate as inimer …”