Linear polystyrenes, rheological

B., 37, 362 (1995). The authors claimed that acetone solutions (5, 10 and 20%, specifically) of a sample that had gel permeation chromatography retention time close to that of a linear polystyrene of 1.1 x 106 molecular mass, had four decades lower viscosity than the corresponding solutions of flexible-chain linear poly(butyl methacrylate). However, in our opinion, neither the examined sample was characterized satisfactorily enough to be referred to as a dendrimer, nor the rheology was described sufficiently enough to draw any conclusions about the solution s flow behavior. Therefore, we refer to this paper here only for reasons of curiosity. 

The lack of mechanical strength for thermoplastic hyperbranched polymers makes them more suitable as additives in thermoplast applications. Hyperbranched polyphenylenes have been shown to act successfully as rheology modifiers when processing linear thermoplastics. A small amount added to polystyrene resulted in reduced melt viscosity [31]. (Sect> 3.1). 

It is not clear why this transition should occur at such a higher level of arm entanglement for polystyrene stars than for other star polymers. This observation is in direct conflict with the standard assumption that through a proper scaling of plateau modulus (Go) and monomeric friction coefficient (0 that rheological behavior should be dependent only on molecular topology and be independent of molecular chemical structure. This standard assumption was demonstrated to hold fairly well for the linear viscoelastic response of well-entangled monodisperse linear polyisoprene, polybutadiene, and polystyrene melts by McLeish and Milner [24]. 

Xing et al. (2000) compared five different techniques for the measurement of interfacial tension in a model polystyrene (PS)/polyamide-6 (PA-6) system at a constant temperature. The techniques include three dynamic methods (the breaking thread, the imbedded fiber retraction, and the retraction of deformed drop), one equilibrium method (the pendant drop), and a rheological method based on linear viscoelastic measurements. The advantages, the limitations, and the difficulties of each technique were discussed and compared. 

The thermal stability of hyperhranched polymers is related to the chemical structure in the same manner as that for linear polymers, eg, aromatic esters are more stable than aliphatic ones. The use of hyperhranched polymers have, however, in some cases been shown to improve the thermal stability when used as additives. An increased thermal stability of polystyrenes has been shown when a small amount of a hyperhranched polyphenylene was used as a rheology modifying additive to polystyrene. 

Polymers with a star-like topology have attracted interest for many years. The rheological behavior in the melt and in solution of starpolymers differs from the behavior of linear polymers [172]. Polystyrene starpolymers with selectively deuterated core or corona chains were investigated by SANS and it was found that the chains are more stretched within the core (or close to the branching point), while the outer parts of the chains follow the single chain behavior of linear polymers [173]. This result confirmed theoretical predictions by Daoud and Cotton [174] and Birshtein et al. [175]. A similar behavior was found for the chain conformations in star-like block copolymer ionomer micelles, which were studied by SANS, too [176]. 

It is now important to calculate the stress exerted by the particles. This stress is equal to aApgfZ. For polystyrene latex particles with radius 1.55 pm and density 1.05 g cm , this stress is equal to 1.6 x 10 Pa. Such stress is lower than the critical stress for most EH EC solutions. In this case, one would expect a correlation between the settling velocity and the zero shear viscosity. This is illustrated in Chapter 7, whereby v/a is plotted versus 7(0). A linear relationship between log( /a ) and log 7(0) is obtained, with a slope of —1, over three decades of viscosity. This indicated that the settling rate is proportional to [7(0)] . Thus, the settling rate of isolated spheres in non-Newtonian (pseudo-plastic) polymer solutions is determined by the zero shear viscosity in which the particles are suspended. As discussed in Chapter 7, on rheological measurements, determination of the zero shear viscosity is not straightforward and requires the use of constant stress rheometers. 

T. Neidhoefer, S. Sioula, N. Hadjichristidis, and M. Wilhelm. Distinguishing linear from star-branched polystyrene solutions with Fourier-transform rheology. Macromol. Rapid Communications, 25 (2004), 1921-1926. 

By means of anionic polymerization, it is possible to produce in the laboratory linear polymers that are nearly monodisperse and have many types of branching such as multi-armed stars and combs and H-shaped molecules. For example, there have been reports of studies of anionically polymerized polystyrene, polybutadiene, and polyisoprene. An example of the anionic polymerization of a branched polymer is the technique of Roovers and Toporowski [22] for making comb polystyrenes. The varieties of model branched polymer that can be produced today by means of block polymerization and coupling chemistries include stars, H-shaped molecules, super-H molecules (multi-armed stars at both ends of a backbone segment), and combs of various types [23]. So-called pom-pom polymers are of special interest, because their rheological behavior has been modeled by McLeish and Larson [24]. These molecules have several arms at each end of a central crossbar, and polybutadienes having this structure have been synthesized [25,26]. 

---