Bulk polymers

Bishop M, Ceperley D, Frisch FI L and Kales M FI 1980 Investigation of static properties of model bulk polymer fluids J Chem. Phys. 72 3228... 

It is generally recognized that the flexibility of a bulk polymer is related to the flexibility of the chains. Chain flexibility is primarily due to torsional motion (changing conformers). Two aspects of chain flexibility are typically examined. One is the barrier involved in determining the lowest-energy conformer from other conformers. The second is the range of conformational motion around the lowest-energy conformation that can be accessed with little or no barrier. There is not yet a clear consensus as to which of these aspects of conformational flexibility is most closely related to bulk flexibility. Researchers are advised to first examine some representative compounds for which the bulk flexibility is known. 

In this chapter we examine the flow behavior of bulk polymers in the liquid state. Such substances are characterized by very high viscosities, a property which is directly traceable to the chain structure of the molecules. All substances are viscous, even low molecular weight gases. The enhancement of this property due to the molecular structure of polymers is one of the most striking features of these materials. 

There are three major aspects of polymer viscosity discussed in this chapter. First, we shall consider the fact that most bulk polymers display shear-dependent viscosity that is, this property does not have a single value but varies with the shearing forces responsible for the flow. Second, the molecular weight dependence of polymer viscosity is examined. We may correctly expect a... 

Of the various parameters introduced in the Eyring theory, only r—or j3, which is directly proportional to it-will be further considered. We shall see that the concept of relaxation time plays a central role in discussing all the deformation properties of bulk polymers and thus warrants further examination, even though we have introduced this quantity through a specific model. 

The subscript 0 on 1 implies 0 conditions, a state of affairs characterized in Chap. 1 by the compensation of chain-excluded volume and solvent effects on coil dimensions. In the present context we are applying this result to bulk polymer with no solvent present. We shall see in Chap. 9, however, that coil dimensions in bulk polymers and in solutions under 0 conditions are the same. 

In the last three chapters we have examined the mechanical properties of bulk polymers. Although the structure of individual molecules has not been our primary concern, we have sought to understand the influence of molecular properties on the mechanical behavior of polymeric materials. We have seen, for example, how the viscosity of a liquid polymer depends on the substituents along the chain backbone, how the elasticity depends on crosslinking, and how the crystallinity depends on the stereoregularity of the polymer. In the preceding chapters we took the existence of these polymers for granted and focused attention on their bulk behavior. In the next three chapters these priorities are reversed Our main concern is some of the reactions which produce polymers and the structures of the products formed. 

We saw in Sec. 2.9 that the viscosity of a bulk polymer is proportional to M, where a is either 1.0 or 3.4, depending on whether the polymer is below or above, respectively, the critical chain length for entanglement. For solutions, a similar result is obtained, only it is [r ] rather than r itself which is proportional to M ... 

Treatment of polymer surfaces to improve their wetting, water repulsion, and adhesive properties is now a standard procedure. The treatment is designed to change the chemistry of the outermost groups in the polymer chain without affecting bulk polymer properties. Any study of the effects of treatment therefore requires a technique that is specific mostly to the outer atomic layers this is why SSIMS is extensively used in this area. 

As mentioned earlier, adhesive bond formation is governed by interfacial processes occurring between the adhering surfaces. These interfacial processes, as summarized by Brown [13] include (1) van der Waals or other non-covalent interactions that form bonds across the interface (2) interdiffusion of polymer chains across the interface and coupling of the interfacial chains with the bulk polymer and (3) formation of primary chemical bonds between chains or molecules at or across the interface. 

As previously mentioned, some urethanes can biodegrade easily by hydrolysis, while others are very resistant to hydrolysis. The purpose of this section is to provide some guidelines to aid the scientist in designing the desired hydrolytic stability of the urethane adhesive. For hydrolysis of a urethane to occur, water must diffuse into the bulk polymer, followed by hydrolysis of the weak link within the urethane adhesive. The two most common sites of attack are the urethane soft segment (polyol) and/or the urethane linkages. Urethanes made from PPG polyols, PTMEG, and poly(butadiene) polyols all have a backbone inherently resistant to hydrolysis. They are usually the first choice for adhesives that will be exposed to moisture. Polyester polyols and polycarbonates may be prone to hydrolytic attack, but this problem can be controlled to some degree by the proper choice of polyol. 

Current (September 1995) international prices (in U.S. dollars per ton) of various bulk polymer in different regions of the world are given in Table 3 for comparison. 

From Table 3 it is clear that PVC is by far the cheapest among the five bulk polymers in the world today. Its unmatched versatility and low cost make PVC commercially one of the most important thermoplastics today. Even in applications in which it is in competition with some of the other bulk polymers its price-performance ratio gives it a slight edge. Despite the attacks from the environmental lobby, PVC continues to retain its commercial significance in the world market. 

Nobile et al. [3] reported that viscosity of a polycar-bonate-TLCP blend can increase or decrease in the same system at the same temperature, depending on the shear condition. At very low shear rates the viscosity was found to increase with TLCP loading, whereas at high shear rates a significant drop was observed. But in all of these cases, the way in which the TLCPs alter the bulk polymer flow is not yet well understood. 

An alternative explanation for the photoinduced absorption in the bulk polymer has been discussed by the Cambridge group [28]. It was shown that the amount of stimulated emission depends critically on the degree of photooxidation of the conjugated polymer. Figure 10-5 compares the stimulated emission of pristine PPV (see Fig. 10-5 a) and its heavily photooxidized counterpart (sec Fig. 10-5b). 

Patterson, G. D. Photon Correlation Spectroscopy of Bulk Polymers. Vol. 48, pp. 125-159. 

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