Poly , Raman spectroscopy

In this review the definition of orientation and orientation functions or orientation averages will be considered in detail. This will be followed by a comprehensive account of the information which can be obtained by three spectroscopic techniques, infra-red and Raman spectroscopy and broad line nuclear magnetic resonance. The use of polarized fluorescence will not be discussed here, but is the subject of a contemporary review article by the author and J. H. Nobbs 1. The present review will be completed by consideration of the information which has been obtained on the development of molecular orientation in polyethylene terephthalate and poly(tetramethylene terephthalate) where there are also clearly defined changes in the conformation of the molecule. In this paper, particular attention will be given to the characterization of biaxially oriented films. Previous reviews of this subject have been given by the author and his colleagues, but have been concerned with discussion of results for uniaxially oriented systems only2,3). 

Normal transmission IRLD can also be used to characterize polymeric fibers, although scattering can induce sloping baselines. Raman spectroscopy then becomes a convenient alternative. Rutledge et al. have recently probed the orientation in electrospun nanofibers composed of a core of Bombyx mori fibroin and an outer shell of poly (ethylene oxide) [24], The orientation values were low, less than 0.1, as is often the case in electrospun fibers. 

The use of organic polymers as conductors and semiconductors in the electronics industry has led to a huge research effort in poly(thiophenes), with a focus on the modification of their electronic properties so that they can behave as both hole and electron conductors. Casado and co-workers [60] have performed combined experimental and theoretical research using Raman spectroscopy on a variety of fluorinated molecules based on oligomers of thiophene, an example of one is shown in Figure 7. 

R. E. Martin, T. Mader, F. Diederich, Monodisperse Poly(triacetylene) Rods Synthesis of a 11.9 nm Long Molecular Wire and Direct Determination of the Effective Conjugation Length by UV/Vis and Raman Spectroscopies , Angew. Chem Int. Ed. Engl. 1999,38, 817-821. 

Emulsion polymerization is used for 10-15% of global polymer production, including such industrially important polymers as poly(acrylonitrile-butadiene-styrene) (ABS), polystyrene, poly(methyl methacrylate), and poly (vinyl acetate) [196]. These are made from aqueous solutions with high concentrations of suspended solids. The important components have unsaturated carbon-carbon double bonds. Raman spectroscopy is well-suited to address these challenges, though the heterogeneity of the mixture sometimes presents challenges. New sample interfaces, such as WAI and transmission mode, that have shown promise in pharmaceutical suspensions are anticipated to help here also. 

M. Tanaka and R.J. Young, Molecular orientation distributions in uniaxiaUy oriented poly(L-lactic acid) films determined by polarized Raman spectroscopy. Macromolecules, 39, 3312-3321 (2006). 

Day, R.J., Robinson, I.M., Zakikhani, M. and Young, R.J. (1987). Raman spectroscopy of stresses high modulus poly(/)-phenylene benzobislhiazole) fibers. Polymer 2S, 1833-1840. 

Significant progress has been achieved in the identification of poly sulfides in non-aqueous solvents, mainly by application of Raman spectroscopy. However, there are... 

Since the late 1960 s a few papers have demonstrated compositional analysis of various polymer systans by Raman spectroscopy. For example, Boerio and Yuann (U) developed a method of analysis for copolymers of glycidyl methacrylate with methyl methacrylate and styrene. Sloane and Bramston-Cook (5) analyzed the terpolymer system poly(methyl methacrylate-co-butadiene-co-styrene). The composition of copolymers of styrene-ethylene dimethacrylate and styrene-divinylbenzene was determined by Stokr et (6). Finally, Water (7) demonstrated that Raman spectroscopy could determine the amount of residual monomer in poly(methyl methacrylate) to the % level. This was subsequently lowered to less than 0.1% (8). In spite of its many advantages, the potential of Raman spectroscopy for the analysis of polymer systems has never been fully exploited. 

Figure 6. Mole percent methyl methacrylate incorporated in poly(methyl)meth-acrylate-co-3-oximino-2-butanone methacrylate) copolymers as a function of monomer feed composition determined by Raman spectroscopy. Key -----------ideality...

Low-frequency Raman spectroscopy (LFRS) has been used to measure the longitudinal acoustic mode (LAM) of semicrystalline diblocks containing poly(ethylene oxide) (Mai et at. 1996 Viras et at. 1988 Yang et at. 1995), The LAM mode frequency is inversely proportional to the crystal stem length, and indicates whether chains are folded or extended. 

There has been a great deal of interest in the UV-visible spectroscopy of the polygermanes, particularly in comparison with the analogous chains that have silicon or tin backbones.41,42 Both conventional and Raman spectroscopy have been employed. One interesting observation is that the symmetrically disubstituted polyfdi- n - a I k y I g e n nanes) exhibit thermochromic transitions at temperatures below those of their polysilane analogues. Another is the conclusion that in poly(di-n-hexylgermane) the side chains adopt trans-planar conformations as in the polysilane counterpart. The two chains are also similar in that both backbones can, under certain circumstances, also adopt planar zig-zag conformations. 

Venancio et al. (2005) used Raman spectroscopy associated UV-vis absorption and AFM to investigate the interaction between HS and poly(o-ethoxyaniline)... 

Another good example of using Raman spectroscopy in the polymer industry is to investigate polymer blends. Raman microimages have been used to investigate the spatial distributions of the components in a blend of brominated poly(isobutylene-co-para-methylstyrene (BIMS) and cis-1-4-polybutadiene (BR) containing silica, zinc stearate, thiate, and other additives (21). A Raman spectrum of a blend is shown in Fig. 7-33. Specific bands can be assigned to BIMS, BR, silica, and zinc stearate. A 10 x 10 xm contour... 

DEGRADATION OF POLY(VINYL CHLORIDE) WITH DIFFERENT ADDITIVES STUDIES BY MICRO RAMAN SPECTROSCOPY... 

---