Nanostructured soft materials open up new opportunities in material design and application, and block copolymer self-assembly is one particularly powerful phenomenon that can be exploited for their synthesis. The advent of controlled/living radical polymerisation (CLRP) has greatly simplified block copolymer synthesis, and versatility towards monomer types and polymer architectures across the different forms of CLRP has vastly expanded the range of functional materials accessible. CLRP-controlled synthesis of block copolymers has been applied in heterogeneous systems, motivated by the numerous process advantages and the position of emulsion polymerisation at the forefront of industrial latex synthesis. In addition to the inherent environmental advantages of heterogeneous routes, the incidence of block copolymer self-assembly within dispersed particles during polymerisation leads to novel nanostructured materials that offer enticing prospects for entirely new applications of block copolymers. Here, we review the range of block copolymers prepared by heterogeneous CLRP techniques, evaluate the methods applied to maximise purity of the products, and summarise the unique nanoscale morphologies resulting from in situ self-assembly, before discussing future opportunities within the field.2

The kinetics of the reaction of hydroxyl radical with 1,3-butadiene at 240-340 K and a total pressure of approximately 1 Torr has been studied using relative rate combined with the discharge flow and mass spectrometer technique. The reaction dynamics of the same reaction has also been investigated using ab initio molecular orbital theory. The rate constant for this reaction was found to be negatively dependent on temperature, with an Arrhenius expression of k1 = (1.58 +/- 0.07) x 10(-11) exp[(436 +/- 13)/T] cm3 molecule(-1) s(-1) (uncertainties taken as 2sigma), which was in good agreement with that reported by Atkinson et al. and Liu et al. at 299-424 K. Mass spectral evidences were found for the addition of OH to both the terminal and the internal carbons of 1,3-butadiene. Our computational results suggest that both addition of OH to 1,3-butadiene and the abstraction of hydrogen atom from 1,3-butadiene by the OH radical are exothermic processes and that the addition of OH to the terminal carbon of the 1,3-butadiene is predicted to have an activation energy of 0.7 kcal mol(-1), being the most energetically favored reaction pathway.

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The dynamics of the reactions of translationally energetic H atoms with BrCN, ClCN, and (CN)2 was studied by determining both the rotational state distribution and the translational energy disposition of the CN product ground vibrational level. The reaction was carried out using H atoms with a most probable translational energy of 92 kJ mol−1. The CN radical was monitored by time- and frequency-resolved absorption spectroscopy using the CN red system (A 2Π←X 2Σ) (2,0) band near 790 nm. Sub-Doppler resolution spectroscopy was used to determine the initial translational temperature of the CN(0,J) product. The fraction of the available reaction exothermicity that appeared as CN(0) rotational energy, fR, for H+XCN→HX+CN was 0.034±0.006, 0.061±0.02, and 0.13±0.007, for X=Br, Cl, and CN, respectively. Likewise, the fraction of the available reaction exothermicity that appeared as relative product translational energy, fT, was 0.52±0.25, 0.52±0.20, and 0.59±0.05, for X=Br, Cl, and CN, respectively. The absolute reaction cross sections for the H+XCN→HX+CN reactions were also measured to be 0.03, 0.02, and 0.3×10−16 cm2 for X=Br, Cl, and CN, respectively.

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We report here the synthesis of well‐defined homopolymer bearing amino acid diamide, poly(N‐acryloyl‐L‐valine N′‐methylamide), via reversible addition fragmentation chain transfer (RAFT) polymerization using alkynyl‐functionalized 2‐dodecylsulfanylthiocarbonylsulfanyl‐2‐methyl‐propionic acid propargyl alcohol ester as chain transfer agent (CTA) and 2,2′‐azobis(isobutyronitrile) as initiator. The effects of a variety of parameters, such as temperature and solvent, on RAFT polymerization were examined to determine the optimal control of the polymerization. The controlled nature of RAFT polymerization was evidenced by the controllable molecular weight and low‐molecular‐weight polydispersity index (Mw/Mn) of resulting homopolymers and further demonstrated to have retained end‐group functionality by the fact of the successful formation of block copolymers from further RAFT polymerization by using the resultant polymer as macro‐CTA, as well as from “click” chemistry. Thermoresponsive property of the prepared polymer was evaluated in terms of the lower critical solution temperature in aqueous solution by measuring the transmittance variation at 500 nm from UV/vis spectroscopy. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3573–3586, 2010

The reaction of the cyano radical (CN) with hydrogen was studied by time-resolved infrared absorption spectroscopy of individual rovibrational states of HCN. The initial vibrational level distribution of HCN(v10v3) was determined by plotting the time dependence of the fractional population of a vibrational level and extrapolating these curves to the origin of time. The experiments were carried out at two temperatures, 293 and 324 K, with similar results. It was estimated that about 50% of the available reaction exothermicity was deposited as vibrational excitation of the HCN product. Surprisingly, the HCN(101) vibrational level received a significant fraction of the observed vibrational population, implying that the CN vibration was not really a spectator bond in the reaction dynamics. Furthermore, the observed HCN(v10v3) vibrations only account for about 27% of the initial HCN population produced in the title reaction. A significant fraction of the product HCN molecules must have been produced with the bending mode excited, likely in combination with the H–C stretch vibrations.

Reported here is a novel approach toward efficient preparation of well‐defined cylindrical brushes polymer (CBPs) with both hydrophobic and hydrophilic side chains connected to the linear backbone by interfacial “click” chemistry in two immiscible solvents. The CBPs with high grafting density of more than 95% and molecular polydispersity (Mw/Mn) less than 1.12 can be readily synthesized using present approach. On contrary, the CBPs synthesized from the “click” reaction in a single solvent in homogenous state have low grafting density of less than 55% and molecular polydispersity (Mw/Mn) more than 1.78. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011