Triblocks, linear

As already mentioned, there has been an extensive amount of studies on the self-assembly of amphiphilic block copolymers in selective solvents over the years. In this section, we will try to give representative examples of these studies divided into two main categories regarding the solvation medium, i.e. amphiphilic copolymers in organic solvents or in aqueous solutions. The latter can be further distinguished in nonionic or ionic containing copolymers. These examples will be limited to the more commonly studied di- and triblock linear copolymers, but concise reviews on the self-assembly of amphiphilic copolymers with more complex non-linear chain architectures can be found elsewhere [98-100]. 

Linear triblock copolymers of the type styrene-butadiene-styrene (SBS) and styrene-isoprene-styrene (SIS) are produced commercially by anionic polymerization through sequential addition of monomers in the reaction chamber [10] as shown below ... 

Abstract This review highlights recent (2000-2004) advances and developments regarding the synthesis of block copolymers with both linear [AB diblocks, ABA and ABC triblocks, ABCD tetrablocks, (AB)n multiblocks etc.] and non-linear structures (star-block, graft, miktoarm star, H-shaped, dendrimer-like and cyclic copolymers). Attention is given only to those synthetic methodologies which lead to well-defined and well-characterized macromolecules. 

Anionic polymerization techniques were also critical for the synthesis of a model cyclic triblock terpolymer [cyclic(S-fo-I-fr-MMA)] [196]. The linear cctw-amino acid precursor S-fr-I-fr-MMA was synthesized by the sequential anionic polymerization of St, I and MMA with 2,2,5,5-tetramethyl-l-(3-lithiopropyl)-l-aza-2,5-disilacyclopentane as the initiator and amine generator, and 4-bromo-l,l,l-trimethoxybutane as a terminator and carboxylic acid generator. Characterization studies of the intermediate materials as well as of the final cyclic terpolymer revealed high molecular and compositional homogeneity. Additional proof for the formation of the cyclic structure was provided by the lower intrinsic viscosity found for the cyclic terpolymer compared to that of the precursor. 

The comparison of a linear PS-fr-PI-fr-PS triblock with its linear analogue was performed by Takano et al. [97]. As in the diblock case the cyclic copolymer exhibits a smaller domain spacing however, the effect is not so pronounced (Table 3). This finding may be explained by the tendency of the ABA triblock to exhibit a higher curvature compared to an AB diblock, which in consequence reduces the differences between a cyclic diblock and its linear ABA counterpart. 

Recently, we have also prepared nanosized polymersomes through self-assembly of star-shaped PEG-b-PLLA block copolymers (eight-arm PEG-b-PLLA) using a film hydration technique [233]. The polymersomes can encapsulate FITC-labeled Dex, as model of a water-soluble macromolecular (bug, into the hydrophilic interior space. The eight-arm PEG-b-PLLA polymersomes showed relatively high stability compared to that of polymersomes of linear PEG-b-PLLA copolymers with the equal volume fraction. Furthermore, we have developed a novel type of polymersome of amphiphilic polyrotaxane (PRX) composed of PLLA-b-PEG-b-PLLA triblock copolymer and a-cyclodextrin (a-CD) [234]. These polymersomes possess unique structures the surface is covered by PRX structures with multiple a-CDs threaded onto the PEG chain. Since the a-CDs are not covalently bound to the PEG chain, they can slide and rotate along the PEG chain, which forms the outer shell of the polymersomes [235,236]. Thus, the polymersomes could be a novel functional biomedical nanomaterial having a dynamic surface. 

The study of both star and linear PS-fr-PEO-fr-PCL triblock copolymers demonstrates the complexity of the crystallization behavior of ABC triblock copolymers and also the multiple possibilities of modifying the crystallization behavior of the block components by changing composition and/or molecular architecture. 

Fig. i Schematic representation of chain conformation in micelles from a linear PEO-PBO diblock copolymers, b linear PEO-PBO-PEO triblock copolymers, c linear PBO-PEO-PBO triblock copolymers and d cyclic PEO-PBO diblock copolymers... 

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