Polymerization-induced thermal self-assembly (PITSA) was conducted using thermoresponsive poly(N-isopropylacrylamide) to result in micelle, worm, and vesicle polymeric morphologies.

Photoinduced living radical polymerization has been employed to synthesize α,ω-telechelic multiblock copolymers of a range of acrylic monomers including methyl acrylate (MA), ethyl acrylate (EA), ethylene glycol methyl ether acrylate (EGA), and solketal acrylate (SA). Under carefully optimized conditions, a well-defined tricosablock (23 blocks) copolymer was obtained ( Đ = 1.18) with high conversion (>98%) achieved throughout all the iterative monomer additions. Crucially, a reduced temperature (15 °C) was found to result in an observed decrease in the dispersities (1.14 vs 1.45) as opposed to when higher temperatures (50 °C) were employed. A number of bifunctional initiators were employed, including ethylene bis­(2-bromoisobutyrate) (EbBiB), a PEG initiator (average M w = 1000 g mol–1), and bis­[2-(2′-bromoisobutyryloxy)­ethyl] disulfide ((BiBOE)2S2), resulting in narrow dispersed multiblock copolymers in various molecular weights (DPn ∼ 2/13/50/100 per block). Impressively, a high molecular weight undecablock (11 blocks) copolymer of M n = 150 000 g mol–1 and Đ = 1.22 was also synthesized. In order to demonstrate the symmetry of the resulting telechelic materials, a well-defined tridecablock (13 blocks, Đ = 1.18, M n = 25 000 g mol–1) was synthesized utilizing a bifunctional disulfide initiator which was cleaved postpolymerization, yielding a narrow disperse polymer at half the molecular weight of the parent polymer ( Đ = 1.10, M n = 12 400 g mol–1).

The controlled polymerization of N-isopropyl acrylamide (NIPAM) is reported in a range of international beers, wine, ciders and spirits utilizing Cu(0)-mediated living radical polymerization (SET-LRP). Highly active Cu(0) is first formed in situ by the rapid disproportionation of [Cu(I)(Me 6-Tren)Br] in the commercial water-alcohol mixtures. Rapid, yet highly controlled, radical polymerization follows (Đ values as low as 1.05) despite the numerous chemicals of diverse functionality present in these solvents e.g. alpha acids, sugars, phenols, terpenoids, flavonoids, tannins, metallo-complexes, anethole etc. The results herein demonstrate the robust nature of the aqueous SET-LRP protocol, underlining its ability to operate efficiently in a wide range of complex chemical environments.

The polymerisation of N-acryloylmorpholine in water is reported utilising Cu(0)-mediated living radical polymerisation (SET-LRP). The inherent instability of [Cu(I) (Me6-Tren)Br] in aqueous solution is exploited via rapid disproportionation to prepare Cu(0) particles and [Cu(II) (Me6-Tren)Br2 ] in situ prior to addition of monomer and initiator. Quantitative conversion is attained within 30 min for various degrees of polymerisation (DPn = 20-640) with SEC showing symmetrical narrow molecular weight distributions (Đ < 1.18) in all cases. Optimised conditions are subsequently applied for the preparation of a diblock copolymer poly(NIPAm)-b-(N-acryloylmorpholine), illustrating the versatility of this approach.

Photoinduced living radical polymerization of acrylates is achieved upon UV irradiation (λ max ≈ 360 nm) in the presence of an aliphatic tertiary amine ligand (Me 6 -Tren) in the presence of low concentrations of CuBr 2 , yielding poly(acrylates) with near perfect retention of end group fidelity. The effect of the nature of the solvent on the rate of polymerization was investigated in order to expand the scope and identify the limitations of the system. Subsequently, a range of acrylic monomers containing hydrophobic and hydrophilic substituents have been screened, including lauryl acrylate, octadecyl acrylate and diethylene glycol ethyl ether acrylate, all of which present low dispersities (Đ ≈ 1.1) at very high conversions. Functional monomers, including glycidyl acrylate and solketal acrylate, were also found to be tolerant to the photomediated reaction. Finally, solketal acrylate was copolymerized with methyl acrylate which, following deprotection of the pendant ketal group, furnished an amphiphilic diblock copolymer. Self-assembly of this block copolymer into polymer micelles in aqueous media was exemplified by dynamic light scattering (DLS) and transmission electron microscopy (TEM).

Despite significant efforts, the design of alkoxyamines for polymerization of methacrylic monomers in a well-controlled fashion with good retention of the active chain ends remains a challenge. Herein, the facile synthesis of several alkoxyamines, which are capable of achieving this long sought-after goal, is reported. Controlled homopolymerization of methyl methacrylate is achieved as determined by a linear increase in molecular weight with conversion and first-order rate plots for various alkoxyamine concentrations. The versatility of the alkoxyamines is further exemplified by the ability to control the homopolymerization of styrene and by synthesis of a block copolymer of a second methacrylate in an efficient chain extension process.

Well-defined fluorescent functional polymers with terminal catechol groups were synthesized by SET-LRP under aqueous conditions for “grafting to” modification of iron oxide nanoparticles.

A note on versions:The version presented here may differ from the published version or, version of record, if you wish to cite this item you are advised to consult the publisher's version. Please see the 'permanent WRAP url' above for details on accessing the published version and note that access may require a subscription. We demonstrate the use of sulfur free reversible addition-fragmentation chain transfer polymerisation (RAFT as a versatile tool for the controlled synthesis of methacrylic block and comb-like copolymers. Sulfur free RAFT (SF-RAFT) utilises vinyl terminated macromonomers obtained via catalytic chain transfer polymerisation (CCTP) of methacrylates as a chain transfer agent (CTA), and thus precluding adverse aspects of the RAFT such as toxicity of dithioesters. We have synthesised a range of narrow dispersity block copolymers (Đ < 1.2) and comb-like macromolecules by employing emulsion polymerisation allowing for the preparation of relatively large quantities (~50 g) of the above mentioned copolymers promptly and straightforwardly. Copolymers were characterised using 1 H NMR, size exclusion chromatography (SEC), thermogravimetric analysis (TGA) and matrix-assisted laser desorption/ionization time of flight mass spectroscopy (MALDI-TOF-MS) techniques.