Polystyrene interface with poly

SBM) as a compatibilizer. As a result of the particular thermodynamic interaction between the relevant blocks and the blend components, a discontinuous and nanoscale distribution of the elastomer at the interface, the so-called raspberry morphology, is observed (Fig. 15). Similar morphologies have also been observed when using triblock terpolymers with hydrogenated middle blocks (polystyrene-W<9ck-poly(ethylene-C0-butylene)-Wock-poly(methyl methacrylate), SEBM). It is this discontinuous interfacial coverage by the elastomer as compared to a continuous layer which allows one to minimize the loss in modulus and to ensure toughening of the PPE/SAN blend [69],... 

Such hydrophilic macromonomers (DPn=7-9) were radically homopolymer-ized and copolymerized with styrene [78] using AIBN as an initiator at 60 °C in deuterated DMSO in order to follow the kinetics directly by NMR analysis. The macromonomer was found to be less reactive than styrene (rM=0.9 for the macromonomer and rs=1.3 for styrene). Polymerization led to amphiphilic graft copolymers with a polystyrene backbone and poly(vinyl alcohol) branches. The hydrophilic macromonomer was also used in emulsion polymerization and copolymerized onto seed polystyrene particles in order to incorporate it at the interface. 

Three homopolymer (diblock copolymer) phase boundary systems have been studied extensively the system of polystyrene (PS) and poly(2-vinylpyridine) (PVP) reinforced with diblock copolymers ofPS-PVP [22,25,28,31-33], the system of poly(methyl methacrylate) (PMMA) and PS reinforced with diblock copolymers of PMMA-PS [17,24,34,35] and the system of PMMA and poly(phe-nylene oxide) (PPO) reinforced by diblock copolymers of PMMA-PS [ 14,36,37]. Phase boundaries between PS and a crosslinked epoxy (XEp) were reinforced with carboxy-terminated PS chains whose -COOH ends reacted with either excess amines or epoxy to form a grafted brush at the interface [38,39]. In a similar manner, interfaces between rubber-modified PS (HIPS) and XEp reinforced with grafted PS-COOH chains have been investigated [40]. 

In a recent pubHcation, Alivisatos and co-workers reported the making of hybrid nanorods-polymer solar cells and their properties [122]. These solar cells were made by spin casting of a solution of both poly(3-hexylthiophene) (hole acceptor) and CdSe nanorods (electron acceptor) onto indium tin oxide glass substrates coated with poly(ethylene dioxythiophene) doped with polystyrene sulfonic acid and aluminum as a top contact. Nanorods have been used in composites so as to improve the carrier mobiHty. Indeed, the latter can be high for some inorganic semiconductors, but it is typically extremely low for conjugated polymers [123]. The use of the nanorods suppHes an interface for the charge transfer as well as a direct path for electrical transport. Also, because of their anisotropy, self-assembly of these nanorods is observed by electron microscopy. It shows... 

Finally, we note that the maximum in the UCFT observed with poly(vinyl alcohol) is readily explicable without the elastic repulsion hypothesis. It merely requires the adsorbed, partially hydrolysed polymer to change from a relatively flat conformation at lower concentrations to a conformation more extended normal to the interface, and thus exhibiting reduced multipoint anchoring, at higher concentrations. This explanation is closely analogous to that proposed by Dobbie et al. (1973) for poly(oxyethylene) attached to polystyrene latices containing surface carboxylic acid groups. 

In contrast to samples with ps<0.1, those with ps > 0.7 exhibit only a spherical morphology of nematic poly[2-(choleste-rylformyl)ethyl methacrylate] spheres in a polystyrene matrix, with no occurrence of PChEMA rods in a polystyrene matrix. As proposed by the researchers, both the curvature of the interface and the small size of the spheres (17 nm) evidently prevent the liquid crystalline block from organizing into its equilibrium smectic A structure, which has a layer distance of 4.5 nm. That is, the equilibrium packing of the mesogens is constrained in the microphase separated re-... 

The first set of experiments that will be considered has examined the ability of random copolymers of styrene and methyl methacrylate to improve the interfacial strength between polystyrene and poly(methyl methacrylate). Using the asymmetric double cantilever beam technique, the researchers have found that a diblock copolymer (50/50 composition, Mw = 282,000) creates an interface with strength of400 J/m2. When utilizing a random copolymer however, it was found that the strongest interface (70% styrene, Mw =... 

A well studied example is given by the poly(oxyethylene-Z locfc-styrene). In case of atactic sequences of polystyrene, only the poly(oxyethylene), POE, can crystallize. A typical morphology of the POE is shown in Fig. 5.55. Single crystals of the copolymer can be grown from a common solvent which keeps both components mobile up to the time of crystallization of the POE-component. Figure 7.53 illustrates a growth spiral out of poly(oxyethylene-fclocfe-styrene), grown at 293 K from a solution of ethylbenzene (AB diblock, 28 wt-% oxyethylene block with a molar mass of about 10,000 Da). The crystal is comparable to the lamellar crystals of Fig. 5.55, i.e., the poly(oxyethylene) crystals are chain-folded with about 2.5 nm amorphous polystyrene layers at the interfaces. 

One might wonder whether it is possible to correlate the interfacial fracture energy of an incompatible polymer pair more precisely to the width of the interface. Such a correlation clearly exists at a qualitative level. For example, polystyrene is substantially less miscible with poly(2-vinyl pyridine) (PVP) than it is with PMMA. This is reflected via equation (4.2.4) in the width of the... 

Fig. 20. Appearance of polystyrene dispersions stabilized with poly(vinyl alcohol) prepared with different initiators. C initiator soluble in the continuous phase, potassium peroxodisulfate D initiator soluble in the disperse phase, dibenzoyl peroxide I initiator located mainly at the interface, PEGA200.

An alternative (and perhaps more efficient) polymeric surfactant is the am-phipathic graft copolymer consisting of a polymeric backbone B (polystyrene or poly(methyl methacrylate)) and several A chains ( teeth ) such as poly(ethylene oxide). The graft copolymer is referred to as a comb stabiliser - the polymer forms a brush at the solid/liquid interface. The copolymer is usually prepared by grafting a macromonomer such as methoxy poly(ethylene oxide) methacrylate with poly(methyl methacrylate). In most cases, some poly(methacrylic acid) is incorporated with the poly(methyl methacrylate) backbone - this leads to reduction of the glass transition of the backbone, making the chain more flexible for adsorption at the solid/liquid interface. Typical commercially available graft copolymers are Atlox 4913 and Hypermer CG-6 supplied by ICI. 

Figure 6.7 Self-assembly of arborescent G1 polystyrene-gra/t-poly (ethylene oxide) copolymers at the air/water interface Copolymers with PEO contents of (a) 15%, (b) 31%, and (c) 74% by weight. The width of each picture is 1.5 pm. (Adapted with permission from G.N. Njikang, L. Cao and M. Gauthier, Self-assembly of arborescent polystyrene-gra/r-poly(ethylene oxide) copolymers at the air/ water interface, Macromolecular Chemistry and Physics, 2008, 209, 907-918. Wiley-VCH Verlag GmbH Co. KGaA.) (Colour version of this figure is available on the book companion web site.)...

Emulsion polymerization is used for 10-15% of global polymer production, including such industrially important polymers as poly(acrylonitrile-butadiene-styrene) (ABS), polystyrene, poly(methyl methacrylate), and poly (vinyl acetate) [196]. These are made from aqueous solutions with high concentrations of suspended solids. The important components have unsaturated carbon-carbon double bonds. Raman spectroscopy is well-suited to address these challenges, though the heterogeneity of the mixture sometimes presents challenges. New sample interfaces, such as WAI and transmission mode, that have shown promise in pharmaceutical suspensions are anticipated to help here also. 

---