Facile synthesis of well-defined hydrophilic methacrylic macromonomers using ATRP and click chemistry

A range of well-defined hydrophilic methacrylic macromonomers has been synthesized by the judicious combination of atom transfer radical polymerization (ATRP) and copper-catalyzed 1,3-dipolar cycloaddition (azide-alkyne click chemistry). An azido a-functionalized ATRP initiator was used to produce well-defined homopolymers with terminal azide functionality via ATRP in protic media at 20 °C, with generally good control being achieved over both target molecular weight and final polydispersity (Mw/Mn = 1.10-1.35). Suitable methacrylic monomers include 2-aminoethyl methacrylate hydrochloride, 2-(diethylamino)ethyl methacrylate, 2-(dimethylamino)ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-(methacryloyloxy)ethyl phosphorylcholine, glycerol monomethacrylate, potassium 3-sulfopropyl methacrylate, and quaternized 2-(dimethylamino)ethyl methacrylate. These homopolymer precursors were then efficiently clicked using either propargyl methacrylate or propargyl acrylate to yield near-monodisperse (meth)acrylate-capped macromonomers with either cationic, anionic, nonionic, or zwitterionic character. Moreover, this generic route to well-defined hydrophilic macromonomers is also suitable for “one-pot” syntheses, as exemplified for 2-hydroxyethyl methacrylate and glycerol monomethacrylate-based macromonomers.

Design, synthesis and thermal behaviour of a series of well-defined clickable and triggerable sulfonate polymers

In the printing industry, the exploitation of triggerable materials that can have their surface properties altered on application of a post-deposition external stimulus has been crucial for the production of robust layers and patterns. To this end, herein, a series of clickable poly(R-alkyl p-styrene sulfonate) homopolymers, with systematically varied thermally-labile protecting groups, has been synthesised via reversible addition-fragmentation chain transfer (RAFT) polymerisation. The polymer range has been designed to offer varied post-deposition thermal treatment to switch them from hydrophobic to hydrophilic. Suitable RAFT conditions have been identified to produce well-defined homopolymers (Đ, Mw/Mn < 1.11 in all cases) at high monomer conversions (>80% for all but one monomer) with controllable molar mass. Poly(p-styrene sulfonate) with an isobutyl protecting group has been shown to be the most readily thermolysed polymer that remains stable at room temperature, and was thus investigated further by incorporation into a diblock copolymer, P3HT-b-PiBSS, by click chemistry. The strategy for preparation of thermal modifiable block copolymers exploiting R-protected p-styrene sulfonates and azide-alkyne click chemistry presented herein allows the design of new, roll-to-roll processable materials for potential application in the printing industry, particularly organic electronics.

Teamwork and well-being:the role of social support

This thesis explores, in a team context, using the Michigan Model, the relationship between social support, stress and well-being outcomes. The studies reported were carried out in Post Office Ltd. Study one examines differences in social support source and type for employees working in teams and quasi teams. Analysis was carried out at the individual level. The results supported previous work on well-being in teams: individuals working in teams report significantly higher levels of well-being, job satisfaction and organisational commitment than those individuals in quasi teams. Members of teams reported greater satisfaction with support from their manager and colleagues, and all types of support compared to members of quasi teams. Manager support and specific types of support mediated the relationship between team working and well-being outcomes. In terms of stressors, satisfaction with manager support and emotional challenge predicted greater influence which was positively related to the well-being outcomes. Study two conducted at the team level builds on relationships established in study one. Stage one explored teamness, the extent to which, along a continuum the team was well-defined. Stage two explored teamness agreement, the extent to which the team agreed on their teamness. The extent to which the Branch Office were a well-defined team had a positive effect on team functioning; participation, innovation and commitment to task excellence. Team functioning was associated with higher levels of satisfaction with manager and team support and all types of support. Working in a well-defined team was associated with job satisfaction, mediated by positive team functioning and social support. Teamness agreement predicted team well-being, clarity of objectives, work demands and satisfaction with reality check. Working in a team was not associated with performance. This thesis advances understanding in the area of team working and processes within teams, advancing understanding of the specifics of social support from different so urces and types of support. The studies reveal the key role of team functional characteri stics in creating the vehicle through which supportive interactions take place. which contribute to positive outcomes associated with working in a well-defined team.