Polysulfobutylbetaine (SBB) (co)polymers, zwitterionic species bearing ammonium and sulfonate groups\ud separated by a butyl spacer in every repeat unit, were prepared through three different synthetic routes\ud and their aqueous solution behaviour was studied. Postpolymerization quaternization of poly[2-(dimethylamino)ethyl\ud methacrylate] with 1,4-butanesultone resulted in incomplete modification due to the low\ud reactivity of this alkylating agent. RAFT radical polymerization of SBB-functional (meth)acrylate monomers\ud and their copolymerization with a sulfopropylbetaine (SPB) methacrylate yielded well-defined (co)polymers\ud with low dispersities 1.13 ≤ ĐM ≤ 1.23 at monomer conversions of 75–92%. For a series of SBB\ud methacrylate homopolymers with increasing degrees of polymerization from 66–186 measured upper\ud critical solution temperature (UCST) cloud points increased from 27–77 °C. Cloud points of statistical\ud SPB-SBB copolymers with similar degrees of polymerization, but varying molar compositions, increased\ud linearly with SBB content offering a simple means of UCST tuning. Additionally, novel SBB acrylamide\ud homo- and copolymers were prepared by postpolymerization modification of poly(pentafluorophenyl\ud acrylate) with an SBB-functional amine and in mixtures with benzylamine as a hydrophobic modifier. In all\ud cases, the SBB (co)polymers had significantly higher UCSTs than their more common SPB counterparts,\ud greatly extending the temperature range of tuneable UCST transitions and making the investigated SBB\ud (co)polymers advantageous for exploiting their ‘smart’ behaviour. In this respect, combining SBB functionality\ud with hydrophobic benzylacrylamide comonomers is presented as a simple means of increasing the\ud maximum salt concentration at which UCST behaviour (which shows an antipolyelectrolyte effect) can be\ud observed, enabling UCST transitions in aqueous solutions containing a physiological concentration (9 g\ud L−1\ud ) of NaCl

RAFT dispersion polymerization (RAFTDP) is used to prepare reactive nanoparticles via the incorporation of Passerini-derived methacrylic comonomers containing pentafluorophenyl (PFP) groups. Copolymerization of 2-(dimethylamino)ethyl methacrylate with a Passerini comonomer gives copolymers suitable as macro-CTAs for ethanolic RAFTDP of 3-phenylpropyl methacrylate. Reaction of the PFP residues with functional thiols offers an approach for preparing surface modified nanoparticles

Soft matter nanoparticles exhibiting rich polymorphism with reactive pentafluorophenyl methacrylate (PFPMA) units in their coronae were prepared via non‐polar reversible addition‐fragmentation chain transfer dispersion polymerization and polymerization‐induced self‐assembly. Poly(stearyl methacrylate‐stat‐PFPMA) macro‐CTAs, containing up to 12 mol % PFPMA, were used in n‐octane and n‐tetradecane for the subsequent copolymerization of 3‐phenylpropyl methacrylate. Both formulations gave the full, common family of nanoparticles (spheres, worms, and vesicles) as determined by transmission electron microscopy. Reaction of the PFP ester repeating units in the coronal layer of spherical nanoparticles with benzylamine, tetrahydrofurfurylamine, N,N‐dimethylethylenediamine, and an amine functional methyl red dye yielded a new library of functional spherical nano‐objects. The success of the nucleophilic acyl substitution reactions was confirmed using a combination of 1H/19F NMR and Fourier transform infrared spectroscopies as well as dynamic light scattering. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 2326–2335