Raman spectroscopy, copolymers composition determination

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...

References to the characterization of emulsion polymers with IR or Raman spectroscopy are not numerous, and IR is used only in very specific cases. Only very few cases of the determination of copolymer composition with IR have been reported. An example where IR is utilized concerns the analysis of poly(methyl acrylate(MA)-co-styrene (S)) copolymers in chloroform at a concentration of 10% w/v [51]. Hergeth and Lange [52] used IR and Raman spectroscopy to study the stracture of core-shell latex particles of poly(vinyl acetate)(PVAc)-polystyrene (PS), and also obtained information about die interfacial layer between the two polymer phases. 

All spectroscopic methods allowing the identification of chemical structures and the quantitative determination of identified chemical functions can be used to determine the composition of a copolymer. Nuclear magnetic resonance is by far the most used method for this purpose, but infrared and Raman spectroscopy can also be used. 

A series of copolymers of D,L-lactide and CL were synthesized by ROP using zinc lactate as a catalyst and carrying out the reaction at 145""C for 8 days. The characterization of PCL and its copolymers with lactides is often done by size exclusion chromatography, DSC, NMR, and stress-strain analysis. Kister et al. used vibrational spectroscopy, particularly Raman spectroscopy, for determination of morphology, conformation, configuration, and composition of the copolymers [49]. Raman spectroscopy thus appeared to be a suitable method for the identification of P(DLA-co-CL) samples directly from solid samples without any special preparation. 

Both IR and Raman spectroscopies are vibrational spectroscopies that provide a unique identification of the substance, or a fingerprint. They are used extensively to determine the composition of materials as discussed by Koenig [3]. Lang et al. [4] showed that IR and Raman provided complementary information about the fibers. They comment that sample preparation is far easier for these methods than the traditional characterization methods based on the solubility of the fibers. In this mode, Raman is used to determine whether a film or fiber is nylon, polyester, polypropylene, cotton, wool, and so forth. Each type of material will have Raman bands specific to the type of polymer of which it is composed. If copolymers are present, the Raman spectra can be used to determine the ratio of comonomers. Many comonomers are strong Raman scatterers (aromatics, double and triple bonds, carbonyls, etc.). Others are weak Raman scatterers (NH, OH, etc.) and are better determined by IR. In either case, an appropriate calibration is required and the spectroscopist needs to make an educated selection between IR and Raman or perhaps use both. 

Kranz and co-workers [126] have shown that acrylonitrile can he determined in styrene - butadiene - acrylonitrile terpolymers via a determination of organic nitrogen by the Kjeldahl procedure. Styrene units can be can be determined by infrared spectroscopy. Butadiene units can be determined by the iodine monochloride procedure. The compositional analysis and details of the microstructure of butadiene - acrylonitrile copolymers can be obtained by Raman spectroscopy [127]. 

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