Star copolymers phase-separate

Block copolymers have peculiar characteristics due to the coexistence of two or several different parts of different chemical compositions within a chain. They can undergo microphase separation transitions from a homogenous phase to a variety of spatially periodic structures [176]. A distinction should be made between star copolymers, where each arm is composed by two or more blocks, and miktoarm polymers, formed by homopolymer arms of different chemical compositions. Floudas et al. [177] recently performed an extensive study of four-... 

Block copolymers consist of chemically distinct polymer chains that are tethered together to form a single macromolecule. If the individual blocks are immiscible when they are unattached, phase separation will also normally occur in the case of the copolymer, with morphologies that depend on the relative composition of the separate block species, and their manner of attachment (diblocks, triblocks, stars, etc.). This is a result of the physical connection of the blocks, which prevents them from separating over distances greater than the contour lengths of the respective blocks. The result is a microphase separation with adjacent domains that are richer in either of the chemical species. 

For quite some time, there have been indications for a phase-separation in the shell of polyelectrolyte block copolymer micelles. Electrophoretic mobility measurements on PS-PMAc [50] indicated that a part of the shell exhibits a considerable higher ionic strength than the surrounding medium. This had been corroborated by fluorescence studies on PS-PMAc [51-53] and PS-P2VP-heteroarm star polymers [54]. According to the steady-state fluorescence and anisotropy decays of fluorophores attached to the ends of the PMAc-blocks, a certain fraction of the fluorophores (probably those on the blocks that were folded back to the core/shell interface) monitored a lower polarity of the environment. Their mobility was substantially restricted. It thus seemed as if the polyelectrolyte corona was phase separated into a dense interior part and a dilute outer part. Further experimental evidence for the existence of a dense interior corona domain has been found in an NMR/SANS-study on poly(methylmethacrylate-fr-acrylic acid) (PMMA-PAAc) micelles [55]. 

The living ROMP reactions of norbomene and norbomene derivatives have been used to make a variety of polymers possessing unusual properties. Copolymerization of selected fimctionalized norbomenes with norbomene has been used to synthesize star polymers and side-chain liquid crystal polymers. This chemistry has also resulted in the preparation of phase separated block copolymers that contain uniform sized metal or semiconductor nanoparticles. The... 

The previously discussed theories were developed for monodisperse diblock copolymers, which are not TPEs. However, Leibler s mean-field theory has been extended to include polydispersity (Leibler and Benoit, 1981) and to include triblock, star, and graft copolymers (Olvera de la Cruz and Sanchez, 1986 Mayes and Olvera de la Cruz, 1989). In the former case, polydispersity corrections tend to lower x N corresponding to the ODT. As would be expected from the analogy between blends and diblocks, triblocks will phase separate at higher xN values than the corresponding diblocks. This theory predicts a monotonic increase in the critical value of x A as the symmetry of the triblock increases, to a maximum of about 18 for the symmetric triblock. Surprisingly, the minimum xN value that separates the order and disordered regions in triblocks does not necessarily correspond to the critical point. 

Self-assembled block copolymers are basically amphilic molecules which contain distinctively different polymers. This block copolymer contains two or more polymers quantitatively in the form of blocks. Some of the block copolymers are polyacrylic acid, polymethylacrylate, polystyrene polyethylene oxide, polybutadiene, polybutylene oxide, poly-2-methyloxazoline, polydimethyl sUoxane, poly-e-caprolactone, polypropylene sulfide, poly-A -isopropylacrylamide, poly-2-vinylpyridine, poly-2-diethylamino ethyl methacrylate, poly-2-(diisopropylamino) ethyl methacrylate, poly-2-(methacryloyloxy) ethyl phosphorylcholine, and polylactic acid. These copolymers contain more than polymers to form certain configurations like linear, branched, patterned. For example, if we take three polymers named A, B, and C, they can be combined to form arrangements AB, BA, AA, BAB, ABCAB, ABCABC, ABABAB, etc. in the form of branched configuration it forms (ABQa, (ABA)a, (AB)4, etc. Depending on the above-mentioned number of blocks, they are named as AB diblock copolymers, ABC triblock copolymers, ABC star block copolymers, etc. The covalent linkage between these different blocks of polymers makes macroscopic phase separation impossible, that is, in its place the phase separation... 

PS was found, by TEM, to be microphase separated as PS cylinders in PI matrix in contrast to a lamellae stmcture expected for linear diblock copolymer of the same composition. Later, more thorough studies with a larger number of samples and covering a wider range of compositions showed that differences exist in the phase diagram for miktoarm star copolymers in comparison to the linear diblocks. The boundaries for the microstrurtures usually encountered in diblocks... 

The polymer-based miscible systems can be either intermolecular mixtures, for instance polymer solutions and blends, or intramolecular mixtures, such as block copolymers, star-shape multi-arm copolymers, grafted copolymers, random copolymers, and gradient copolymers with a composition gradient from one chain end to the other. Polymer-based miscible systems can phase separate into segregated phases with stable interfaces, or crystallize into crystalline ordered phases. In other words, there are two types of phase transitions, phase separation and crystallization. Under proper thermodynamic conditions, two phase transitions may occur simultaneously. The interplay of these two transitions will dictate the final morphology of the system. In the following, we will choose polymer solutions as typical examples to introduce the polymer-based miscible systems. 

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