Degree of polymerization weight

There are also some empirical equations for describing the yields of products formed in the cracking reactions of polymers. One of them is the Atkinson and McCaffrey kinetic model, which derives the weight loss of polymer for their initial degree of polymerization, weight of sample and reaction rate. As a matter of fact the reaction rate constant is calculated by using a first-order kinetic equation [33, 34]. 

Simultaneous minimization of (1) reaction time, (2) polydispersity index for desired value of monomer conversion and (3) degree of polymerization. Weighting method The resulting single objective optimization problem was solved by SQP, GA and a hybrid of the two. Based on more than 100 optimization runs, all the three methods were concluded to be trustworthy. Curteanu et al (2006)... 

The second category of polymerization reactions does not involve a chain reaction and is divided into two groups poly addition and poly condensation [4]. In botli reactions, tire growth of a polymer chains proceeds by reactions between molecules of all degrees of polymerization. In polycondensations a low-molecular-weight product L is eliminated, while polyadditions occur witliout elimination ... 

In homopolymers all tire constituents (monomers) are identical, and hence tire interactions between tire monomers and between tire monomers and tire solvent have the same functional fonn. To describe tire shapes of a homopolymer (in the limit of large molecular weight) it is sufficient to model tire chain as a sequence of connected beads. Such a model can be used to describe tire shapes tliat a chain can adopt in various solvent conditions. A measure of shape is tire dimension of tire chain as a function of the degree of polymerization, N. If N is large tlien tire precise chemical details do not affect tire way tire size scales witli N [10]. In such a description a homopolymer is characterized in tenns of a single parameter tliat essentially characterizes tire effective interaction between tire beads, which is obtained by integrating over tire solvent coordinates. 

The degree of polymerization of a polymer is simply the number of repeat units in a molecule. The degree of polymerization n is given by the ratio of the molecular weight of the polymer to the molecular weight of the repeat unit ... 

We began this section with an inquiry into how to define the size of a polymer molecule. In addition to the molecular weight or the degree of polymerization, some linear dimension which characterizes the molecule could also be used for this purpose. For purposes of orientation, let us again consider a hydrocarbon molecule stretched out to its full length but without any bond distortion. There are several features to note about this situation ... 

Note that the average weight per repeat unit could be used to evaluate the overall degree of polymerization of this terpolymer. For example, if the molecular weight were 43,000, the corresponding degree of polymerization would be... 

The high molecular weight of a polymer is one of the most immediate consequences of the chain structure of these molecules. As indicated in Sec. 1.2, it is also the basis for describing the size of the polymer molecule, either directly or through the degree of polymerization. Most methods for the determination... 

As should be expected, both (fg ) and r show the same dependence on the degree of polymerization or molecular weight. Since the radius of gyration can be determined experimentally through the measurement of viscosity or light scattering, it is through this quantity that we shall approach the evaluation of 1. 

It should be noted that a log-log plot condenses the data considerably and that the transition between a first-power and a 3.4-power dependence occurs over a modest range rather than at a precise cutoff. Nevertheless, the transition is read from the intersection of two lines and is identified as occurring at a degree of polymerization or molecular weight designated n, or, respectively. 

The next step in the development of a model is to postulate a perfect network. By definition, a perfect network has no free chain ends. An actual network will contain dangling ends, but it is easier to begin with the perfect case and subsequently correct it to a more realistic picture. We define v as the number of subchains contained in this perfect network, a subchain being the portion of chain between the crosslink points. The molecular weight and degree of polymerization of the chain between crosslinks are defined to be Mj, and n, respectively. Note that these same symbols were used in the last chapter with different definitions. 

Table 4.1 lists values of as well as AH and ASf per mole of repeat units for several polymers. A variety of experiments and methods of analysis have been used to evaluate these data, and because of an assortment of experimental and theoretical approximations, the values should be regarded as approximate. We assume s T . In general, both AH and ASf may be broken into contributions Ho and So which are independent of molecular weight and increments AHf and ASf for each repeat unit in the chain. Therefore AHf = Hq + n AHf j, where n is the degree of polymerization. In the limit of n AHf = n AHf j and ASf = n ASf j, so T = AHf j/ASf j. The values of AHf j and ASf j in Table 4.1 are expressed per mole of repeat units on this basis. Since no simple trends exist within these data, the entries in Table 4.1 appear in numbered sets, and some observations concerning these sets are listed here ... 

The number average degree of polymerization for these mixtures is easily obtained by recalling the definition of the average from Sec. 1.8. It is given by the sum of all possible n values, with each multiplied by its appropriate weighting factor, provided by Eq. (5.24) ... 

The degree of polymerization values in the two combining radicals can have any value, and the molecular weight of the product molecule will be considerably higher on the average than the radicals so terminated. The polymeric product molecule contains two initiator fragments per molecule by this mode of termination. 

High molecular weight polymers or gums are made from cyclotrisdoxane monomer and base catalyst. In order to achieve a good peroxide-curable gum, vinyl groups are added at 0.1 to 0.6% by copolymerization with methylvinylcyclosiloxanes. Gum polymers have a degree of polymerization (DP) of about 5000 and are useful for manufacture of fluorosiUcone mbber. In order to achieve the gum state, the polymerization must be conducted in a kineticaHy controlled manner because of the rapid depolymerization rate of fluorosiUcone. The expected thermodynamic end point of such a process is the conversion of cyclotrisdoxane to polymer and then rapid reversion of the polymer to cyclotetrasdoxane [429-67 ]. Careful control of the monomer purity, reaction time, reaction temperature, and method for quenching the base catalyst are essential for rehable gum production. 

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