Amorphous polystyrene

The nature of the hard domains differs for the various block copolymers. The amorphous polystyrene blocks in the ABA block copolymers are hard because the glass transition temperature (100°C) is considerably above ambient temperature, i.e., the polystyrene blocks are in the glassy state. However, there is some controversy about the nature of the hard domains in the various multiblock copolymers. The polyurethane blocks in the polyester-polyurethane and polyether-polyurethane copolymers have a glass transition temperature above ambient temperature but also derive their hard behavior from hydrogen-bonding and low levels of crystallinity. The aromatic polyester (usually terephthalate) blocks in the polyether-polyester multiblock copolymer appear to derive their hardness entirely from crystallinity. 

Molecular-Weight and Cooling-Rate Dependence of Simulated Tg for Amorphous Polystyrene. 

Yeh,G.S.Y. Order in amorphous polystyrenes as revealed by electron diffraction and diffraction microscopy. J. Macromol. ScL-Phys. B6,451-464 (1972). 

We shall examine the range of stability of the ordered structures of copolymers containing an amorphous polystyrene, polybutadiene or poly(ethyl methacrylate) block and acrystallizable polyethylene oxide) (PEO) or poly(e-caprolactone) (PCL) crystallizable block and the factors that determine the existence and the geometrical parameters of such periodic structures. 

The Polymer. Amorphous Polystyrene. All of the expandable polystyrene referred to above is the amorphous type that is obtained by free radical initiation. This polymer is completely noncrystalline, and in the absence of impurities such as monomer and blowing agent it exhibits a glass-transition temperature of about 100°C. Both the rate of expansion and the extent of expansion are enhanced by reducing molecular weight, but the foam becomes less resistant to collapse on further steaming (63). Other polymeric modifications are discussed below. 

The difference in softening temperatures for amorphous and semi-crystalline polymers becomes also clear from Fig. 13.3, where the Young moduli of amorphous and of semicrystalline polystyrene are illustrated. For amorphous polystyrene the two HDTs appear to be 92 and 97 °C and for the semi-crystalline polystyrene 99 and 114 °C. It has to be mentioned, however, that the curves in Fig. 13.3 are the so-called 10 s moduli, i.e. measured after 10 s of stress relaxation, every point at a specific temperature. The measurements in the softening experiments are not in agreement with the determination of the standard Young modulus. 

Investigations on a block-copolymer of PEG and polystyrene also showed that in the solid state, the amorphous polystyrene occupies a space between two PEG blocks 179). These observations suggested a similar two-phase model for the PEG-peptides in the solid state which explains the high retention of crystallinity of the polymer even when it is bound to amorphous peptides 180). 

Crystalline and amorphous polystyrene were chosen for the XPS study. But, the two recorded valence band spectra do not... 

Enhanced property demands in the packaging sector and also in the electric/ electronic and automotive sectors require improved product properties. Homogeneously miscible blends with, e.g., polyphenylene ether (PPE) combine the excellent processability of the amorphous polystyrene with the thermal stabilty of its blend partners. 

The polyethylene latexes obtained in the different emulsion polymerization procedures using the various aforementioned nickel(II) complexes display average particle diameters of 100 to 600 nm. A number of anionic surfactants or neutral stabilizers are suitable, i.e. compatible with the catalysts and capable of stabilizing the latex. Solids contents of up to 30% have been reported to date. A typical TEM image is shown in Fig. 7.2. By comparison to smooth, spherical latex particles of amorphous polystyrene as a well studied hydrocarbon polymer prepared by free-radical emulsion polymerization, the ruggedness of the particles shown can be rationalized by their high degree of crystallinity. 

The structure of amorphous polystyrene has been examined using X-rays (1 6) and the analysis suggests that phenyl-phenyl contacts dominate with both inter and intra molecular contacts resulting in stacking effects. Such an interaction is consistent with the stability derived from face to face configurations (17,18). Thus... 

Bernes, A., Etude de la metastabilite d un polymere amorphe (polystyrene atactique) en fonction de son histoire thermodynamique par spectroscopie enthalpique dielectrique, Ph.D. thesis, Toulouse University, France, 1985. 

Fig. 4.4. Spectral factor/ fj(0) in the spin-diffusion rate constant calculated from the experimental separated-local-field spectrum of amorphous polystyrene [21, 30] for (a) a static sample, and (b) for a spectrum obtained under slow-MAS conditions. (Adapted from Ref. [21], with permission).

Foams (cellular structures) made by expanding a material by growing bubbles in it [11]. A foam has at least two components. At a macroscopic scale, there are the solid and liquid phases. The solid phase can be a polymer, ceramic or metal. The fluid phase is a gas in most synthetic foams, and a liquid in most natural foams. At a microscopic scale, the solid phase may itself consist of several components. For example, the solid phase of an amorphous polystyrene foam has only one component. On the other hand, the solid phase of a polyethylene foam or a flexible polyurethane foam typically has two components. These components are the crystalline and amorphous phases in polyethylene foams, and the hard and soft phases formed by the phase separation of the hard and soft segment blocks in flexible polyurethane foams. The solid phase of a polyurethane foam may, in fact, have even more than two components, since additional reinforcing components such as styrene-acrylonitrile copolymer or polyurea particles are often incorporated [12,13]. The solid is always a continuous phase in a foam. Foams can generally be classified as follows, based on whether the fluid phase is co-continuous with the solid phase ... 

Subsequently the polybutadiene segment was functionalized by quantitatively converting the olefin double bonds of the 1,2-polybutadiene block via a hydroboration reaction to hydroxyl functions. In the last step various azobenzene-chromophores were attached via a polymeranalogous reaction. The synthesis and characterization as well as photophysical aspects of block copolymers based on an amorphous polystyrene block and a functionalized 1,2-polybutadiene block... 

The process involves transesterification (catalyst, 200 °C) followed by polycondensation (250 °C, second stage. Morphological studies show the presence of crystalline (mp 190-200 °C) polyester lamellae in a continuous amorphous phase. In contrast to the A-B-A thermoplastic elastomers where the domains are formed from amorphous polystyrene segments, the domains here are formed from crystalline hard segments containing the 1,4-glycol polyester moiety. 

Styrene is one of the oldest and most studied monomers. It spontaneously generates free radials upon heating above 100 °C and polymerizes yielding amorphous polystyrene (PS). Styrene can also be polymerized by other mechanisms (anionic, cationic, or Zeigler-Natta) with the aid of chemical initiators. Commercially, over twenty billion pounds of PS are produced annually worldwide. All of this polystyrene is produced via free radical (FR) chemistry, and mostly via continuous solution polymerization processes. The commercial preference for the continuous solution process is due mainly to economic factors. Non-solution polymerization processes (suspension and emulsion) have lower reactor efficiency (product/reactor volume) due to reactor volume occupied by the water which adds to the manufacturing cost. 

The results presented here illustrate the general feasibility of this technique. They relate primarily to the behavior of thermal and current noise in the glass transition (Tg) or melting (Tm) region of an amorphous (polystyrene) and a crystalline (HD-polyethylene (HDPE)) polymer rendered conductive by the addition of minor amounts of carbon black, and further they relate to the noise of aqueous solutions of certain polymers during Couette flow. Because of experimental diflBculties, noise measurements on solid polymers during deformation and flow have not yet produced useful results. 

Song, H.-H., and Roe, R.-J., Structural change accompanying volume change in amorphous polystyrene as studied by small and intermediate angle x-ray scattering. Macromolecules, 20, 2723-2732 (1987). 

Conte, P., Carotenuto, G., Piccolo, A., Perlo, R, and Nicolais, L., NMR-investigation of the mechanism of silver mercaptide thermolysis in amorphous polystyrene, J. Mater. Chem., 17, 201-205 (2007). 

For our experimental studies on polymer crystallization we used low molecular weight (Mw) poly(ethylene oxide) (PEO), either as a homopolymer or attached to an amorphous polystyrene or hydrogenated polybutadiene block. These block copolymers are abbreviated by PS-PEO and PB, -PEO, respectively. PEO is a weU-investigated polymer [5,19,36,37]. Molecular details of all investigated polymers are given in Table 1. 

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