Displays block copolymers

SBS and SIS can be subsequently hydrogenated to form SEBS and SEPS, respectively. SEBS is obtained from SBS with a higher vinyl content (typically around 30%) in order to avoid crystallization of the mid-block. The properties of all four of these common styrenic block copolymers are displayed in Table 2. 

Dithiocarbamatc 16 has been used to prepare low dispersity PMAA ( Mw 1 Mn-1.2).52 Photopolymerization of S in the presence of dithiocarbamate 16 also displays some living characteristics (molecular weights that increase with conversion, ability to make block copolymer). However, 17 appears to behave as a conventional initiator in S polymerization.53 The difference in behavior was attributed to the relatively poor leaving group ability of the 2-carboxyprop-2-yI radical. This hypothesis is supported by MO calculations. Dithiocarbamatc 17 was used to control polymerizations of MMA,54 HEMA54 and NIPAM.5... 

The thermal properties of block copolymers are similar to physical blends of the same polymer segments. Each distinct phase of the copolymer displays unique thermal transitions, such as a glass transition and/or a crystalline melting point. The thermal transitions of the different phases are affected by the degree of intermixing between the phases. 

The use of lightly crosslinked polymers did result in hydrophilic surfaces (contact angle 50°, c-PI, 0.2 M PhTD). However, the surfaces displayed severe cracking after 5 days. Although qualitatively they appeared to remain hydrophilic, reliable contact angle measurements on these surfaces were impossible. Also, the use of a styrene-butadiene-styrene triblock copolymer thermoplastic elastomer did not show improved permanence of the hydrophilicity over other polydienes treated with PhTD. The block copolymer film was cast from toluene, and transmission electron microscopy showed that the continuous phase was the polybutadiene portion of the copolymer. Both polystyrene and polybutadiene domains are present at the surface. This would probably limit the maximum hydrophilicity obtainable since the RTD reagents are not expected to modify the polystyrene domains. 

Triblock copolymers, as shown in Fig. 5.8 d), comprise a central homopolymer block of one type, the ends of which are attached to homopolymer chains of another type. As with other block copolymers, the components of triblocks may be compatible or incompatible, which will strongly influence their properties. Of particular interest are triblocks with incompatible sequences, the middle block of which is rubbery, and the end blocks of which are glassy and form the minor phase. When such polymers phase-segregate, it is possible for the end blocks of a single molecule to be incorporated into separate domains. Thus, a number of rubbery mid-block chains connect the glassy phases to one another. These materials display rubber-like properties, with the glassy domains acting as physical crosslinks. Examples of such materials are polystyrene/isoprene/polystyrene and polystyrene/polybutadiene/polystyrene triblock copolymers. 

It should be re-emphasized that although our block copolymers do not display spherulitic morphology when they are compression molded, they are nevertheless crystalline. Hence, this indicates that under this mode of film preparation, aggregation into well developed superstructure is apparently kinetically limited. 

The dynamic mechanical behavior of the block copolymers of HB and HI are typified by the results obtained for the HIBI series which are given in Figure 15A and B which display spectra for different composition ratios. The transition behavior of the HBIB series is so similar that it will not be repeated here. The samples used for this study were compression molded and they all had been stored at room temperature between one to two months before use. The experiments were run at 110 Hz. The behavior of HB, represented by HIBI 100, is similar to that given in Figure 14B. 

Table 14 The block copolymers in the library are displayed in the table by molar masses and by the volume fractions of PSt, -[Ru]-, and poly(ethylene tated between brackets)...

Thanks to their multiphase constitution, block copolymers have the originality to add advantageously the properties of their constitutive sequences. These very attractive materials can display novel properties for new technological applications. In this respect, thermoplastic elastomers are demonstrated examples (l, 2, 3) they are currently used without any modification as elastic bands, stair treads, solings in the footwear industry, impact resistance or flexibility improvers for polystyrene, polypropylene and polyethylene whereas significant developments as adhesives and adherends are to be noted (5.). 

In solution, block copolymers display interesting colloidal and interfacial properties. They can be used as emulsifying agents in water-oil and oil-oil systems (6 ). In the later case, the oil phases are solid and they give rise to polymeric alloys (7.) or they are liquid and they allow the preparation of latexes in organic medium (8 ). However, the molecular structure of block copolymers based on polybutadiene PB (70 ) and polystyrene PS behave as thermoplastic elastomers when engaged in multiblock (PB-PS)n or triblock (PS-PB-PS) structures but never when implied in inverse triblock or diblock arrangements. Similarly the... 

Koberstein and coworkers121 have examined the effects of a polydimethylsiloxane-polystyrene (PDMS-PS) block copolymer on the interfacial tensions of blends of PDMS and polystyrene. As little as 0.002 wt% of the copolymer, added to the siloxane phase, was sufficient to lower the interfacial tension by 82% in the case of a blend of polystyrene (Afn = 4,000) and PDMS (Mn = 4,500). No further reduction in interfacial tension was observed at higher copolymer levels due to micelle formation. Riess122 has polymerized styrene in the presence of a silicon oil and a polydimethylsiloxane-polystyrene block copolymer to obtain a polystyrene in which 0.1-1 pm droplets of silicone oil are dispersed. This material displayed a lowered coefficient of kinetic friction on steel compared to pure polystyrene. 

Recently, a new class of inhibitors (nonionic polymer surfactants) was identified as promising agents for drug formulations. These compounds are two- or three-block copolymers arranged in a linear ABA or AB structure. The A block is a hydrophilic polyethylene oxide) chain. The B block can be a hydrophobic lipid (in copolymers BRIJs, MYRJs, Tritons, Tweens, and Chremophor) or a poly(propylene oxide) chain (in copolymers Pluronics [BASF Corp., N.J., USA] and CRL-1606). Pluronic block copolymers with various numbers of hydrophilic EO (,n) and hydrophobic PO (in) units are characterized by distinct hydrophilic-lipophilic balance (HLB). Due to their amphiphilic character these copolymers display surfactant properties including ability to interact with hydrophobic surfaces and biological membranes. In aqueous solutions with concentrations above the CMC, these copolymers self-assemble into micelles. 

Figure 18a,b displays SFM images of SV films that have been prepared from chloroform and from toluene solutions, respectively. The mixed pattern of featureless areas and round-shaped stripes in Fig. 18a can be identified as in-plane lamella and perpendicular-oriented lamellae, respectively. The microstructure prepared from toluene solutions (Fig. 18b) is attributed to P2VP micelles surrounded by the PS shell. The micelle morphology is a result of the SV self-assembly in a selective solvent [119], We have made use of this morphological difference to study the microstructure response to solvent uptake by block copolymer films. 

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