Conformation solid polymers

Figure 9.15 Schematic illustration of size exclusion in a cylindrical pore (a) for spherical particles of radius R and (b) for a flexible chain, showing allowed (solid) and forbidden (broken) conformations of polymer.

I. Bitsanis, G. ten Brinke. A lattice Monte Carlo study of long chain conformations at a solid polymer-melt interface. J Chem Phys 99 3100-3111, 1993. 

Starting from the assumption that the geometry relaxation after excitation is of primary importance with respect to the luminescence response, we decided to employ a solid polymer matrix to suppress conformational changes of the oligomers. For the measurements, dilute blends with polysulfone as the transparent host matrix were prepared. In Figure 16-13, the PL decay curves for the two cyano compounds in both chloroform and polysulfone are presented, as are the PL spectra of Ooct-OPV5-CN in chloroform and polysulfone [69J. 

Solid-State Electrical Characterization of Conformal, Ultrathin Polymer Dielectrics... 

In recent years new NMR techniques offering broad applications in stereochemical analysis have come into use. A prominent example is 2D-NMR (both 2D-resolved and 2D-correlated spectroscopy), which has been extensively applied to biopolymers (149-151). Its use with synthetic polymers has, until now, been limited to but a few cases (152, 153). A further technique, cross-polarization magic-angle spinning spectroscopy (CP-MAS NMR) will be discussed in the section on conformational analysis of solid polymers. 

In IR spectra of secondary amides, which exist mainly in the trans conformation, the free NH stretching vibration observed in dilute solutions occurs near 3500-3400 cm-1. In more concentrated solutions and in solid samples, the free NH band is replaced by multiple bands in the 3330-3060 cm-1 region. Multiple bands are observed since the amide group can bond to produce dimers with an s-cis conformation and polymers with an s-trans conformation. 

As discussed earlier, solid polymers can be distinguished into amorphous and the semicrystalline categories. Amorphous solid polymers are either in the glassy state, or - with chain cross linking - in the rubbery state. The usual model of the macromolecule in the amorphous state is the "random coil". Also in polymer melts the "random coil" is the usual model. The fact, however, that melts of semi-crystalline molecules, although very viscous, show rapid crystallisation when cooled, might be an indication that the conformation of a polymer molecule in such a melt is more nearly an irregularly folded molecule than it is a completely random coil. 

The system described in this investigation is polystyrene-14C adsorbed on Graphon carbon black (graphitized Spheron 6) from six solvents comprising a wide spectrum from good to poor solvent power. Well-characterized materials were selected to elucidate the conformation of polymer molecules at the solid/liquid interface. So far two models have been postulated to describe the conformation of the adsorbed polymer molecules at the solid/liquid interface (9, 13, 14, 18, 19, 21, 27). In the first model the polymer assumes a loop or coil structure in which only a fraction of the polymer segments are attached directly at the interface, and in the second model the polymer forms a relatively flat and compressed interfacial layer with many segments attached to the solid substrate. 

Electrochemically stimulated conformational relaxation model (ESCR model) — This model [i, ii] describes the relaxation phenomena occurring during the charging and discharging of -> conducting polymers. It assumes that applying an anodic -> overpotential to a neutral conjugated polymer, as a first step, an expansion of the closed polymeric structure occurs. In this way, partial oxidation takes place and counter ions from the solution enter the solid polymer under the influence of an electrical field at those points of the polymer/electrolyte... 

The secondary structure, such as a conformation, is studied mainly by solid-state NMR.2 In the solid state, NMR chemical shift is characteristic of specific conformations because the internal rotation around the chemical bonds is restricted. This shows that the NMR chemical shift can be used for elucidating the conformation of polymers in the solid state. In the amorphous phase, the conformation of the polymer chain is not fixed above Tg. Even in such a case, NMR chemical shift and the relaxation parameters can give us useful information such as the averaged conformation or the dynamics of the exchange. Solid-state NMR can also provide information about the crystalline structures, which are classified under the higher order structures through NMR chemical shift, since for most polymers, different crystalline structures accompany conformational changes which affect their NMR chemical shift. 

We shall consider only some results of investigation of complex polymer systems by method of EPR-spectroscopy obtained recently (results obtained earlier were considered in details in works [2, 3]). We shall discuss possibilities of method of EPR-spectroscopy of spin marks and probes for determination of macromolecules conformation in solid state, and also the results of investigation of molecular dynamics and organization of micelle systems -complexes polyelectrolyte-SAS. We shall also discuss some results obtained with the use of method of EPR-spectroscopy and its modification - the method of EPR-tomography for revealing of particularities of spatial distribution of active sites resulted from process of thermo-oxidative destruction of solid polymers. 

Presented here results allow making conclusion that method of EPR-spectroscopy of spin markers is effective method of determination of macromolecules conformation in solid state. This method may significantly enlarge information obtained by other methods, in particular by method of neutrons scattering. The advantage of this method is in the fact that it may give information about conformational state of comparatively small parts of solid polymers chains. 

The fundamental questions are What is the microscopic mechanism or driving force for the transition, and what physical factors are important Two distinct possibilities have been advanced side-chain crystallization (5, 6, 17-19), which is postulated to induce polymer backbone ordering, and conformation-dependent polymer-solvent interactions that arise explicitly from electron delocalization and that stabilize an ordered rodlike conformation (20-24). Side-chain crystallization remains a qualitative suggestion that has not been developed to the point where it has predictive power and can be critically tested. However, in the solid state, the enhanced importance of packing effects makes such a mechanism more plausible (18, 19). 

Solid polymers can occur in the amorphous or crystalline state. Polymers in the amorphous state are characterized by a disordered arrangement of the macromolecular chains, which adopt conformations corresponding to statistical coils. The crystalline state is characterized by a long-range three-dimensional order (order extending to distances of hundreds or thousands... 

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