Poly dipoles

The term polymer is derived from the Greek words poly and meros, meaning many parts. We noted in the last section that the existence of these parts was acknowledged before the nature of the interaction which held them together was known. Today we realize that ordinary covalent bonds are the intramolecular forces which keep the polymer molecule intact. In addition, the usual type of intermolecular forces—hydrogen bonds, dipole-dipole interactions, and London forces—hold assemblies of these molecules together in the bulk state. The only thing that is remarkable about these molecules is their size, but that feature is remarkable indeed. 

A solubihty parameter of 24.5-24.7 MPa / [12.0-12.1 (cal/cm ) ] has been calculated for PVF using room temperature swelling data (69). The polymer lost solvent to evaporation more rapidly than free solvent alone when exposed to air. This was ascribed to reestabUshment of favorable dipole—dipole interactions within the polymer. Infrared spectral shifts for poly(methyl methacrylate) in PVF have been interpreted as evidence of favorable acid—base interactions involving the H from CHF units (70). This is consistent with the greater absorption of pyridine than methyl acetate despite a closer solubihty parameter match with methyl acetate. 

Polymer/Polymer Complexes. PVP complexes with other polymers capable of interacting by hydrogen-bonding, ion-dipole, or dispersion forces. For example mixing of PVP with poly(acryHc acid) (PAA) in aqueous solution results in immediate precipitation of an insoluble complex (113). Addition of base results in dismption of hydrogen bonding and dissolution (114—116). Complexes with a variety of poly-acids (117) and polyphenols (118) have been reported. The interest in compatibiHty on a molecular level, an interesting phenomenon rarely found to exist between dissimilar polymers, is favored by the abiHty of PVP to form polymer/polymer complexes. 

In the case of polar polymers the situation is more complex, since there are a large number of dipoles attached to one chain. These dipoles may either be attached to the main chain (as with poly(vinyl chloride), polyesters and polycarbonates) or the polar groups may not be directly attached to the main chain and the dipoles may, to some extent, rotate independently of it, e.g. as with poly(methyl methacrylate). 

When dipoles are directly attached to the chain their movement will obviously depend on the ability of chain segments to move. Thus the dipole polarisation effect will be much less below the glass transition temperature, than above it Figure 6.4). For this reason unplasticised PVC, poly(ethylene terephthalate) and the bis-phenol A polycarbonates are better high-frequency insulators at room temperature, which is below the glass temperature of each of these polymers, than would be expected in polymers of similar polarity but with the polar groups in the side chains. 

In the case of polymer molecules where the dipoles are not directly attached to the main chain, segmental movement of the chain is not essential for dipole polarisation and dipole movement is possible at temperatures below the glass transition temperature. Such materials are less effective as electrical insulators at temperatures in the glassy range. With many of these polymers, e.g., poly(methyl methacrylate), there are two or more maxima in the power factor-temperature curve for a given frequency. The presence of two such maxima is due to the different orientation times of the dipoles with and without associated segmental motion of the main chain. 

Although it is a polar polymer, its electrical insulating properties at room temperature are good even at high frequencies owing to the fact that since room temperature is well below the transition temperature dipole orientation is severely restricted. Some data on the crystallinity of poly(ethylene terephthalate) are presented in Table 25.5. 

We can divide commodity plastics into two classes excellent and moderate insulators. Polymers that have negligible polar character, typically those containing only carbon-carbon and carbon-hydrogen bonds, fall into the first class. This group includes polyethylene, polypropylene, and polystyrene. Polymers made from polar monomers are typically modest insulators, due to the interaction of their dipoles with electrical fields. We can further divide moderate insulators into those that have dipoles that involve backbone atoms, such as polyvinyl chloride and polyamides, and those with polar bonds remote from the backbone, such as poly(methyl methacrylate) and poly(vinyl acetate). Dipoles involving backbone atoms are less susceptible to alignment with an electrical field than those remote from the backbone. 

Poly(aminoborane) has a relatively simple structure, as shown in Figure 9. Jacquemin and co-workers [63] performed a comprehensive set of calculations to investigate the infrared spectra, vertical excitation energies, geometries, atomic charges and dipole moments as a function of conformation. A variety of theoretical methods were employed, including Hartree-Fock, MP2 and... 

Cheam, T. C., and S. Krimm. 1985. Infrared Intensities of Amide Modes in N-methyl-acetamide and Poly(Glycine I) From Ab Initio Calculations of Dipole Moment Derivatives of N-methylacetamide. J. Chem. Phys. 82, 1631-1641. 

In table I we present the molar Kerr constants and mean square dipole moments of three fluorinated polymers, poly (trifluoroethylene) (PFjE), polylvinylidene fluoride) (PVF2) and poly(fluoromethylene) (PFM), dissolved in p-dioxane. The results show the sensitivity of mK to the degree and type of fluorination varying over an order of magnitude and also changing sign. Calculations of mK and for comparison are in progress (5). 

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