Triblock Copolymer Architectures

Choi S, Lee KM, Han CD (2004) Effects of triblock copolymer architecture and the degree of functionalization on the oiganoclay dispersion and rheology of nanocomposites. Macromolecules 37 7649-7662... 

We present here a simple experiment, conceived to test both the reptation model and the minor chain model, by Welp et al. [50] and Agrawal et al. [51-53]. Consider the HDH/DHD interface formed with two layers of polystyrene with chain architectures shown in Fig. 5. In one of the layers, the central 50% of the chain is deuterated. This constitutes a triblock copolymer of labeled and normal polystyrene, which is, denoted HDH. In the second layer, the labeling has been reversed so that the two end fractions of the chain are deuterated, denoted by DHD. At temperatures above the glass transition temperature of the polystyrene ( 100°C), the polymer chains begin to interdiffuse across the... 

Block copolymers can contain crystalline or amorphous hard blocks. Examples of crystalline block copolymers are polyurethanes (e.g. B.F. Goodrich s Estane line), polyether esters (e.g. Dupont s Hytrel polymers), polyether amides (e.g. Atofina s Pebax grades). Polyurethanes have enjoyed limited utility due to their relatively low thermal stability use temperatures must be kept below 275°F, due to the reversibility of the urethane linkage. Recently, polyurethanes with stability at 350°F for nearly 100 h have been claimed [2]. Polyether esters and polyether amides have been explored for PSA applications where their heat and plasticizer resistance is a benefit [3]. However, the high price of these materials and their multiblock architecture have limited their use. All of these crystalline block copolymers consist of multiblocks with relatively short, amorphous, polyether or polyester mid-blocks. Consequently they can not be diluted as extensively with tackifiers and diluents as styrenic triblock copolymers. Thereby it is more difficult to obtain strong, yet soft adhesives — the primary goals of adding rubber to hot melts. 

Hysteresis Behavior. The hysteresis behavior of the HBIB triblock copolymers are given in Figure 13A and of that of the inverted HIBI block copolymer is given in Figure 13B. The difference in the behavior of these two series of block copolymers is tremendous. The origin of these differences are again directly related to the morphology and the architecture of the polymers. 

The term star-block copolymer is used for a star architecture in which each arm is a diblock. The influence of chain topology on mechanical and morphological properties was investigated for copolymers composed of PS and PB with a constant styrene content of = 0.74 by Michler s group (Fig. 32) [101,102], While hexagonally packed cylinders of PB in a PS matrix were observed in a symmetric PS-fo-PB-fr-PS triblock copolymer, an L phase... 

In the last few years there have been new creative methods of preparation of novel hydrophilic polymers and hydrogels that may represent the future in drug delivery applications. The focus in these studies has been the development of polymeric structures with precise molecular architectures. Stupp et al. (1997) synthesized self-assembled triblock copolymer, nanostructures that may have very promising applications in controlled drug delivery. Novel biodegradable polymers, such as polyrotaxanes, have been developed that have particularly exciting molecular assemblies for drug delivery (Ooya and Yui, 1997). 

We use polystyrene-Z>-polybutadiene block copolymers as the starting material with preformed polymer architecture. These polymers are comparatively cheap and easily accessible.1 For the present problems a series of narrowly distributed polystyrene-6-polybutadiene block copolymers with rather different molecular weights were synthesized via anionic polymerization (Figure 10.4, Table 10.1). As a test for the modification of technological products, a commercial triblock copolymer was also used. 

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. 

In order to explore the properties that may be obtained by hybridizing the linear and dendritic architectural states, both diblock and triblock copolymer... 

A series of interesting block copolymer architectures has also been prepared by Zhang et al. In a first paper, the synthesis of H-shaped triblock copolymers was demonstrated from enzymatically obtained PCL diol after end-functionalization with a difunctional ATRP initiator [40]. This allowed the growth of two PS chains from each end of the telechelic PCL. When methanol instead of glycol was used as the initiator in the initial enzymatic CL polymerization, a PCL with one hydroxyl endgroup was obtained. Functionalization of this endgroup with the difunctional ATRP initiator and subsequent ATRP of styrene or GMA resulted in Y-shaped polymers (Scheme 3) [41, 42]. 

The mechanical and thermal properties of a range of poly(ethylene)/ poly(ethylene-propylene) (PE/PEP) copolymers have been examined by Mohajer et al. (1982). They studied the effect of variation of composition and copolymer architecture on the polymer properties by synthesizing a range of PE-PEP-PE and PEP-PE-PEP triblocks and PE-PF.P diblocks with high molecular weights (M > 200 kg mol (.The crystallinity, density and melting enthalpy for all copolymers were found to be linearly dependent on the PE content, indicating microphase separation of PE and rubbery PEP in the solid state. The... 

Since the relaxation mechanisms characteristic of the constituent blocks will be associated with separate distributions of relaxation times, the simple time-temperature (or frequency-temperature) superposition applicable to most amorphous homopolymers and random copolymers cannot apply to block copolymers, even if each block separately shows thermorheologically simple behavior. Block copolymers, in contrast to the polymethacrylates studied by Ferry and co-workers, are not singlephase systems. They form, however, felicitous models for studying materials with multiple transitions because their molecular architecture can be shaped with considerable freedom. We report here on a study of time—temperature superposition in a commercially available triblock copolymer rubber determined in tensile relaxation and creep. 

Reynhout, I. C., Cornelissen, J., Nolte, R. J. M., Self-assembled architectures from biohybrid triblock copolymers. J. Am. 

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