The graft-through synthesis of Janus graft block copolymers (GBCPs) from branched macromonomers composed of various combinations of homopolymers is presented. Self-assembly of GBCPs resulted in ordered nanostructures with ultra-small domain sizes down to 2.8 nm (half-pitch). The grafted architecture introduces an additional parameter, the backbone length, which enables control over the thermomechanical properties and processability of the GBCPs independently of their self-assembled nanostructures. The simple synthetic route to GBCPs and the possibility of using a variety of polymer combinations contribute to the universality of this technique.

Polymerization-induced self-assembly was exploited to investigate the self-assembly behavior of liquid crystalline triblock copolymers with long solvophilic chains.

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which are undesirable if remained in the final product, and can only be eliminated by additional processing steps that will produce extra waste streams. More importantly, conventional latexes coagulated this way are very difficult or impossible to redisperse in water due to the deactivation of particle surface surfactants caused by added chemicals, especially after drying into powder form. [1a,b] Hence, the facile latex coagulation and removal of water without adding chemicals can provide substantial economic and environmental benefits.As a green stimuli-responsive trigger, CO 2 has recently received increasing interests over other stimuli, due to its many advantages including nontoxicity, inexpensiveness, easiness to operate, and more importantly, no salt accumulation. [2] Several research groups, including Jessop, Cunningham, Zhu, Zhao, Feng, and our group, [3] have designed various CO 2 -triggered smart systems, such as CO 2 -responsive self-assemblies, hydrogels, surfaces, emulsions, and others, by exploiting the reversible hydrophilic-hydrophobic transition via CO 2 and inert gas treatment in water. In particular, we have previously utilized CO 2 -switchable block copolymers to create "breathing" polymersomes that could reversibly swell and shrink through CO 2 /N 2 bubbling, in order to achieve size-selective release, separation and reaction. [3c,f ] Moreover, we have also developed CO 2 -triggered nanofibrous membranes with tunable oil/water wettability, realizing highly controlled and reversible oil/water separation via CO 2 /N 2 treatment. [3k] Meanwhile, reversibly coagulable and redispersible latexes and emulsions can be achieved via different CO 2 -switchable approaches, such as CO 2 -switchable initiators, [4] surfactants, [3b,5] comonomers, [6] surfmers, [7] and others. [8] In fact, Jessop and co-workers were the first to use CO 2 -switchable long chain alkyl and aryl amidine surfactants to prepare CO 2 -switchable latexes, which could be coagulated via inert gas treatment and heating, and later be redispersed via CO 2 treatment and sonication. [3b,5a,b] However, due to the structural limitations of these molecular surfactants that can only physically adsorb on the latex particle surface, they might be desorbed during the destabilization process, thus reducing the latex redispersibility. Additionally, CO 2 -switchable latex systems based on amidine chemistry have two main drawbacks: first is the high cost The ability to reversibly switch between latex solution and dried powder can potentially provide major economic and environmental benefits to emulsion related industries, especially in the substantial reduction of energy consumption and cost from the transportation and handling of latex water content. Here, a versatile CO 2 /N 2 -switchable latex system with high reversibility is developed by combining a CO 2 -responsive polymeric surfactant and a CO 2 -responsive initiator. In particular, the coagulability from latexes to dried powder and redispersibility back to solution form are syste...

Three different structural types of polymeric dispersants were synthesised, optimised and systematically compared over SiO2 particle dispersion, developing structure–performance relationships.