Chengmin Hou

Simple approach towards fabrication of highly durable and robust superhydrophobic cotton fabric from functional diblock copolymer

We report here a simple and reproducible strategy for fabricating highly durable and robust superhydrophobic cotton fabrics (SCFs) from a series of functional diblock copolymers. These diblock copolymers consisted of both poly(glycidyl methacrylate) (PGMA) and poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) blocks that were synthesized via sequential atom transfer radical polymerization (ATRP). While the PTFEMA block provides the low surface free energy, the PGMA block serves as an anchor and forms covalent bonds with the surfaces of cotton fibers. These covalent bonds are formed via the epoxy ring-opening reaction between the epoxy groups of the PGMA block and the hydroxyl groups on the surface of the cotton fiber, and self-crosslinking of epoxy groups from PGMA chains. Structures exhibiting nano- and microscale roughness were created in one-step by combining copolymer-based nanobumps onto surfaces of micro-sized fibers of the cotton fabric, as confirmed by SEM and AFM analysis. The modified cotton fabrics show excellent water repellency with water contact angles (WCAs) of ∼163° and water sliding angles (WSAs) of ∼3° under optimized conditions. Since the low-fluorinated PTFEMA chains are chemically bound to the cotton fibers, the SCFs possess long-term stability, ultra-high durability and robustness. In particular, these SCFs withstood mechanical abrasion by sandpaper, strong laundering conditions, ultrasonication treatment in tetrahydrofuran (THF) or trifluorotoluene (TFT), soaking in a wide range of organic solvents, as well as acidic and basic aqueous solutions, exposure to UV-irradiation and even refluxing in TFT or THF.

Emulsion and nanocapsules of ternary graft copolymers

Alkyne end-tagged poly(ethylene glycol) methyl ether, polystyrene, and poly(tert-butyl acrylate) (denoted as MPEG–CCH, PS–CCH, and PtBA–CCH, respectively) were grafted randomly onto a (PGMA–N3) backbone via “click” chemistry to produce a series of ternary graft copolymers PGMA-g-(MPEG-r-PtBA-r-PS). The selective hydrolysis of the PtBA chains into poly(acrylic acid) (PAA) yielded PGMA-g-(MPEG-r-PAA-r-PS). Since MPEG and PAA were soluble in water while PS was soluble in decahydronaphthalene (DN), the graft copolymers were good surfactants for emulsifying DN in water. Various factors affecting the emulsification were examined, including the stirring rate, the copolymer composition, and the concentration. Crosslinking of the PAA chains, which were distributed among MPEG chains in the coronas of the emulsion droplets, with a diamine produced a novel structure – “nanocapsules” bearing partially crosslinked coronas.

Synthesis of poly(2-hydroxyethyl methacrylate) end-capped with asymmetric functional groups via atom transfer radical polymerization

Poly(2-hydroxyethyl methacrylate) (PHEMA) end-capped with living chloride and alkyne groups was synthesized via ATRP of HEMA using CuCl/CuCl2/2,2′-bipyridine as a catalyst in a solvent mixture of methanol and 2-butanone. The effects of parameters including the initiator, solvent, temperature and initial monomer to initiator ratios on polymerization were studied in terms of polymerization kinetics, the degree of polymerization (DP) and molar mass dispersity (Đ) of the resulting PHEMA polymer. ATRP of HEMA using propargyl 2-bromoisobutyrate (PBiB) as an initiator was poorly controlled, but those using 3-(trimethylsilyl)propargyl 2-bromoisobutyrate (TMSPBiB) and 3-(triisopropysilyl)propargyl 2-bromoisobutyrate (TiPSPBiB) as initiators were well-controlled. Moreover, the apparent propagation rate constant for ATRP of HEMA using the TMSPBiB initiator was higher than that using the TiPSPBiB initiator. The solvent mixture of methanol–2-butanone at different compositions greatly affected the polymerization controllability. A high molecular weight PHEMA sample with a DP of 1000 and a Đ of 1.34 was obtained under appropriate conditions. The poly(2-hydroxyethyl methacrylate)-block-poly(butyl acrylate) (PHEMA-b-PBA) diblock copolymer was prepared through ATRP of BA using (CH3)3Si–CC–PHEMA–Cl as a macroinitiator. The methoxyl polyethylene glycol-block-poly(2-hydroxyethyl methacrylate) (MPEG-b-PHEMA) diblock copolymer was prepared by click reaction between MPEG-N3 and HCC–PHEMA–Cl. These two reactions demonstrated the reactivity of the asymmetric functional groups end-capping the PHEMA, and further provided modular examples for the synthesis of a novel well-defined (co)polymer with complex architectures.

Superparamagnetic-Oil-Filled Nanocapsules of a Ternary Graft Copolymer

Stearic and oleic acid-coated Fe3O4 nanoparticles were dispersed in decahydronaphthalene (DN). This oil phase was dispersed in water using ternary graft copolymer poly(glycidyl methacrylate)-graft-[polystyrene-ran-(methoxy polyethylene glycol)-ran-poly(2-cinnamoyloxyethyl methacrylate)] or PGMA-g-(PS-r-MPEG-r-PCEMA) to yield capsules. The walls of these capsules were composed of PCEMA chains that were soluble in neither water nor DN, and the DN-soluble PS chains stretched into the droplet phase and the water-soluble MPEG chains extended into the aqueous phase. Structurally stable capsules were prepared by photolyzing the capsules with UV light to cross-link the PCEMA layer. Both the magnetite particles and the magnetite-containing capsules were superparamagnetic. The sizes of the capsules increased as they were loaded with more magnetite nanoparticles, reaching a maximal loading of ~0.5 mg of ligated magnetite nanoparticles per mg of copolymer. But the radii of the capsules were always <100 nm. Thus, a novel nanomaterial--superparamagnetic-oil-filled polymer nanocapsules--was prepared. The more heavily loaded capsules were readily captured by a magnet and could be redispersed via shaking. Although the cross-linked capsules survived this capturing and redispersing treatment many times, the un-cross-linked capsules ruptured after four cycles. These results suggest the potential to tailor-make capsules with tunable wall stability for magnetically controlled release applications.