Of branched polymers

We must be careful in assessing the experimental results on the viscosity of branched polymers. If we compare two polymers of identical molecular weight, one branched and the other unbranched, it is possible that the branched one would show lower viscosity. Two considerations enter the picture here. First, since the side chains contribute to the molecular weight, the backbone chain... 

Commercial polyfvinyl alcohol) (e.g. Gelvatol, Elvanol, Mowiol and Rhodo-viol) is available in a number of grades which differ in molecular weight and in the residual acetate content. Because alcoholysis will cause scission of branched polymers at the points where branching has proceeded via the acetate group, polyfvinyl alcohol) polymer will have a lower molecular weight than the poly (vinyl acetate) from which it is made. 

Relationships between dilute solution viscosity and MW have been determined for many hyperbranched systems and the Mark-Houwink constant typically varies between 0.5 and 0.2, depending on the DB. In contrast, the exponent is typically in the region of 0.6-0.8 for linear homopolymers in a good solvent with a random coil conformation. The contraction factors [84], g=< g >branched/ <-Rg >iinear. =[ l]branched/[ l]iinear. are another Way of cxprcssing the compact structure of branched polymers. Experimentally, g is computed from the intrinsic viscosity ratio at constant MW. The contraction factor can be expressed as the averaged value over the MWD or as a continuous fraction of MW. 

Examples of branched polymers of the type under consideration are few. Polymers prepared by Friedel-Crafts condensation of benzyl halides doubtless are properly described as such... 

Characterization of Branched Polymers by Size Exclusion Chromatography with Light Scattering Detection... 

A simple algorithm [17] makes it possible to find the probability of any fragment of macromolecules of Gordonian polymers. Comparison of these probabilities with the data obtained by NMR spectroscopy provides the possibility to evaluate the adequacy of a chosen kinetic model of a synthesis process of a particular polymer specimen. The above-mentioned probabilities are also involved in the expressions for the glass transition temperature and some structure-additive properties of branched polymers [18,19]. 

Chandrasekhar, V. Polymer Solid Electrolytes Synthesis and Structure, Vol 135, pp, 139-206 Charleux, B Faust R Synthesis of Branched Polymers by Cationic Polymerization, Vol. 142, pp. 1-70. 

Freire, /. /. Conformational Properties of Branched Polymers Theory and Simulations. VoL 143, pp. 35-112. 

McLeish, T.C.B., Milner, S. T Entangled Dynamics and Melt Flow of Branched Polymers. VoL 143, pp. 195-256. 

Star shaped macromolecules are polymers, where the one end of f > 2 (f functionality of the star) linear chains is chemically attached by covalent bonds to a small central linker unit, are the simplest form of branched polymers. Modern anionic polymerization techniques allow us to synthesize star systems with a large number of nearly monodisperse arms [133, 134],... 

A viscosity online detector in a size exclusion chromatography (SEC) instrument allows for a universal calibration for polymers with known K- and a-values. For polymers that are only soluble at high temperature, e.g., polyolefines, high-temperature detectors are available, which can be operated up to 200°C. In addition to molar mass measurements, viscosity detectors have also been employed successfully to obtain structural information of branched polymers [28]. 

In their study of branched PSA, Maniar et al. (1990) found that the molecular architecture of branched polymers affects the release kinetics in a variety of ways. They found that the branched polymers degraded faster than linear PSA of comparable molecular weight (Maniar et al., 1990). They also noted that drug (morphine) release profiles were more characteristic of bulk erosion than surface erosion An initial lag time during which very little drug was released was associated with the time required for water to swell the polymer. This was followed by a period of relatively fast release, which tapered off as the device disintegrated. The polymer matrix lost its mechanical integrity before the release experiment was complete (Maniar et al., 1990). Despite the increase... 

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