Star-shaped block copolymer

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. 

In these two decades remarkable progress has been made in the development of excellent catalysts for living and stereospecific acetylene polymerizations (10,26-28). The r-conjugated polymers prepared by the sequential polsrmerization are strictly limited to polyacetylenes, except for only a few examples. Thus, synthesis of tailor-made conjugated macromolecules such as end-functionalized polymers, block copolymers, star-shaped polymers is possible only in the case of substituted acetylenes. 

Block copolymers are polymers constituted of at least two different monomers arranged in a specific manner - they could be diblock, triblock, multi-block, linear, star shaped, etc. Those based on styrene and butadiene, SB or SBS, are the earliest to be applied and studied, as well as the largest as far as the volume of production is concerned (Holden et al. 1967). 

Fig. 2. Selected architectures of block copolymers (a) diblock (b) triblock (c) comb copolymer consisting of flexible chains (d) rod-coil diblock copolymer consisting of a rodlike block and a coil-like block (e) hairyrods, i.e., comb-block copolymers consisting of rodlike backbone and coil-like side chains and (f) LC coil with a side-chain liquid crystalline (LC) block and a flexible block. Many other variations have been introduced, such as multiblock copolymers, block copolymers consisting of several rodlike blocks, or star-shaped block copolymers. Comb-coil block copolymers with dense packing of side chains are also denoted as molecular bottle brushes, as is illustrated in (g) by a simulated structure of an isolated molecule dissolved in a solvent. (Courtesy of Mika Saariaho.)...

More recent examples include end-functionalized multiarmed poly(vinyl ether) (44), MVE/styrene block copolymers (45), and star-shaped polymers (46—48). With this remarkable control over polymer architecture, the growth of future commercial appHcations seems entirely likely. 

Transparent toughened polystyrene polymers are produced by blending polystyrene with SBS block copolymers (see Section 11.8). During the 1970s and 1980s most development was with block copolymers with a radial (or star) shape. Two types were developed block copolymers with a central butadiene block, and block copolymers with a central polystyrene block. 

Closely related to these but thermoplastic rather than rubber-like in character are the K-resins developed hy Phillips. These resins comprise star-shaped butadiene-styrene block copolymers containing about 75% styrene and, like SBS thermoplastic elastomers, are produced by sequential anionic polymerisation (see Chapter 2). 

The purpose of this review is to show how anionic polymerization techniques have successfully contributed to the synthesis of a great variety of tailor-made polymer species Homopolymers of controlled molecular weight, co-functional polymers including macromonomers, cyclic macromolecules, star-shaped polymers and model networks, block copolymers and graft copolymers. 

Kahayashi N. and Yoshida M., Star-shaped block copolymers and production process thereof, US Patent 6310175, 2001. 

Yijin X. and Caiyaun P., Block and star-hlock copolymers by mechanism transformation. 3. S-(PTHF-PSt)4 and S-(PTHF-PSt-PMMA)4 from living CROP to ATRP, Macromolecules, 33, 4750, 2000. Feldthusen J., Ivan B., and Mueller A.H.E., Synthesis of linear and star-shaped block copolymers of isobutylene and methacrylates hy combination of living cationic and anionic polymerizations. Macromolecules, 31, 578, 1998. 

The paper is organized in the following way In Section 2, the principles of quasi-elastic neutron scattering are introduced, and the method of NSE is shortly outlined. Section 3 deals with the polymer dynamics in dense environments, addressing in particular the influence and origin of entanglements. In Section 4, polymer networks are treated. Section 5 reports on the dynamics of linear homo- and block copolymers, of cyclic and star-shaped polymers in dilute and semi-dilute solutions, respectively. Finally, Section 6 summarizes the conclusions and gives an outlook. 

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. 

The oxocarbenium perchlorate C(CH20CH2CH2C0+C104 )4 was employed as a tetrafunctional initiator for the synthesis of PTHF 4-arm stars [146]. The living ends were subsequently reacted either with sodium bromoacetate or bromoisobutyryl chloride. The end-capping reaction was not efficient in the first case (lower than 45%). Therefore, the second procedure was the method of choice for the synthesis of the bromoisobutyryl star-shaped macroinitiators. In the presence of CuCl/bpy the ATRP of styrene was initiated in bulk, leading to the formation of (PTHF-fc-PS)4 star-block copolymers. Further addition of MMA provided the (PTHF-fr-PS-fc-PMMA)4 star-block terpolymers. Relatively narrow molecular weight distributions were obtained with this synthetic procedure. 

In analogy to linear-block copolymers different cases can be distinguished when blending asymmetric miktoarm (PS-PI)n-PS and H-shaped (PS-PI)3-PS-(PI-PS)3 copolymers with homopolymer PS [122]. If the latter s molecular weight is lower than the respective PS block, a transition from the L structure to hexagonally packed cylinders without observation of an intervening cubic morphology is observed in the case of the (PS-PI)n-PS types. If the H-shaped (PS-PI)3-PS-(PI-PS)3 star-block copolymer is blended with 30% to... 

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. 

Meier MAR, FUali M, Gohy J-F, Schubert US (2006) Star-shaped block copolymer stabilized palladium nanoparticles for effident catalytic Heck cross-coupling reactions. J Mater Chem 16 3001-3006... 

The composition of the star-shaped block copolymer is easily determined by proton NMR analysis from this and the mean number average molecular weight (Mn) of the sequence PA, Mn of the polyether component can be calculated. The later is very similar to the value from membrane osometry. Hydroxyl end group of PA(P0)2 star-shaped block copolymers have been titrated and their mean number per copolymer (1.85) agrees with the presence of two polyoxirane branches. On the average, the polydispersity of the star-shaped block copolymers varies between 1.2 and 1.3 (Figure 6). 

Surface Activity of the PA(PO), Star-Shaped Block Copolymers... 

Riess demonstrated recently that poly(styrene-b-oxirane) copolymers could act as non-ionic surfactants and lead to water/ toluene microemulsions (29, 30). Using isopropanol as cosurfactant, both 0/W and W/0 microemulsions are obtained (3l). This is a very important conclusion, since PO based diblock copolymers give rise only to 0/W microemulsions under the same experimental conditions (8, 31,). In this respect the "branched structure" of the PO hydrophilic component could favor a decrease in the packing density of the inverse micelle forming molecular and explain the different behavior of the linear and star-shaped PS/PO block copolymers in the W/0 microemulsification process. 

The criterion of stability (R) is the constant limit value of the emulsified volume percentage at 20°C (32, 32.). It appears that 7/3 water toluene emulsions are more efficiently stabilized by star-shaped block copolymers whereas linear block copolymers give better results for 3/7 water toluene emulsions the stability of the l/l water toluene emulsions seems to be insensitive to the molecular architecture of PTBS/PO block copolymers. 

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