Polymeric materials, molecular

T.H. Richardson, Functional Organic and Polymeric Materials Molecular Functionality - Macroscopic Reality, John Wiley Sons, Chichester, UK, 2000. 

Near-infrared (NIR) is routinely used to qualify monomers prior to polymerization reactions. It is used to measure the kinetics of polymer onset and can be used to detect end-point completion and initiator compound levels in polymerization reactions. NIR spectro- scopy can also be used to sort polymers and to control the quality of incoming raw monomers and finished polymeric materials. Molecular spectroscopy using NIR and IR measurement techniques is often used for competitive analysis and to determine thermal or photo-induced oxidation or degradation reactions in polymers. In general, NIR spectroscopy is valuable for polymer identification, characterization, and quantitation. NIR spectroscopy can be completed for in situ process applications where no sample preparation is a requirement, and where rugged optical systems are a necessity. Some of the earliest work in applying IR and NIR spectroscopy to polymer characterization is found in References 1 to 11. 

The successful preparation of polymers is achieved only if tire macromolecules are stable. Polymers are often prepared in solution where entropy destabilizes large molecular assemblies. Therefore, monomers have to be strongly bonded togetlier. These links are best realized by covalent bonds. Moreover, reaction kinetics favourable to polymeric materials must be fast, so tliat high-molecular-weight materials can be produced in a reasonable time. The polymerization reaction must also be fast compared to side reactions tliat often hinder or preclude tire fonnation of the desired product. 

The various elastic and viscoelastic phenomena we discuss in this chapter will be developed in stages. We begin with the simplest the case of a sample that displays a purely elastic response when deformed by simple elongation. On the basis of Hooke s law, we expect that the force of deformation—the stress—and the distortion that results-the strain-will be directly proportional, at least for small deformations. In addition, the energy spent to produce the deformation is recoverable The material snaps back when the force is released. We are interested in the molecular origin of this property for polymeric materials but, before we can get to that, we need to define the variables more quantitatively. 

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. 

The picture presented above for confinement of the excitons within the device is for the EM layer sandwiched between the HTL and ETL. The EM need not be a discrete layer in the OLED, however, for exciton confinement to occur. Alternatively, the EM can consist of a luminescent molecule doped (- 1%) into a polymeric or molecular host material (40,41,54,55). So long as the energy gap (or band gap) of the host is higher than that of the EM dopant, excitons will be effectively trapped or confined on the dopant molecules leading to improved EL efficiency. An example of such a dopant-based device... 

Adsorption systems employing molecular sieves are available for feed gases having low acid gas concentrations. Another option is based on the use of polymeric, semipermeable membranes which rely on the higher solubiHties and diffusion rates of carbon dioxide and hydrogen sulfide in the polymeric material relative to methane for membrane selectivity and separation of the various constituents. Membrane units have been designed that are effective at small and medium flow rates for the bulk removal of carbon dioxide. 

Table 1. Hole Mobilities of Selected Molecular and Polymeric Materials ...

Table 2. p-QjCt, and E and Some Hole Mobilities, cm /V s, of Selected Molecular and Polymeric Materials ... 

The most commonly used scale inhibitors are low molecular weight acrylate polymers and organophosphoms compounds (phosphonates). Both classes of materials function as threshold inhibitors however, the polymeric materials are more effective dispersants. Selection of a scale control agent depends on the precipitating species and its degree of supersaturation. The most effective scale control programs use both a precipitation inhibitor and a dispersant. In some cases this can be achieved with a single component (eg, polymers used to inhibit calcium phosphate at near neutral pH). 

J. R. Reynolds and M. Pomerantz, in T. A. Skotheim, ed., Electroresponsipe Molecular and Polymeric Materials, Marcel Dekker, New York, 1991. 

There is a whole science called molecular architecture devoted to making all sorts of chains and trying to arrange them in all sorts of ways to make the final material. There are currently thousands of different polymeric materials, all having different properties - and new ones are under development. This sounds like bad news, but we need only a few six basic polymers account for almost 95% of all current production. We will meet them later. 

In numerous applications of polymeric materials multilayers of films are used. This practice is found in microelectronic, aeronautical, and biomedical applications to name a few. Developing good adhesion between these layers requires interdiffusion of the molecules at the interfaces between the layers over size scales comparable to the molecular diameter (tens of nm). In addition, these interfaces are buried within the specimen. Aside from this practical aspect, interdififlision over short distances holds the key for critically evaluating current theories of polymer difllision. Theories of polymer interdiffusion predict specific shapes for the concentration profile of segments across the interface as a function of time. Interdiffiision studies on bilayered specimen comprised of a layer of polystyrene (PS) on a layer of perdeuterated (PS) d-PS, can be used as a model system that will capture the fundamental physics of the problem. Initially, the bilayer will have a sharp interface, which upon annealing will broaden with time. 

In addition to plastics materials, many fibres, surface coatings and rubbers are also basically high polymers, whilst in nature itself there is an abundance of polymeric material. Proteins, cellulose, starch, lignin and natural rubber are high polymers. The detailed structures of these materials are complex and highly sophisticated in comparison the synthetic polymers produced by man are crude in the quality of their molecular architecture. 

Plasticizers are substances (usually low molecular weight diluents) that are incorporated into polymeric materials to improve their workability and increase flexibility. Polymeric plasticizers are low glass transition temperature (Tg) poly-... 

It is desirable that the plasticizer compounded with a polymer be permanently retained. Loss of plasticizer changes the properties of a given formulation, and can be produced by volatilization, extraction or migration. The volatility of a plasticizer in a formulation can be related to the surface area, thickness of the polymeric material, and viscosity (e.g. molecular weight) of the plasticizer itself. 

Obviously, these polymerized materials are sold as mixtures of compounds having an average molecular weight. For example, polyethylene glycol-400 (PEG400) is a... 

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