Polymer analysis mass spectrometry

Application of mass spectrometry to analysis of additives in polymers is mainly used as a qualitative tool and relates to three main areas ... 

The first synthesis of molecules of this kind was reported independently by Vogtle [52] and Hall [51] and both involved condensation of 34 with a range of diazamacrocycles 37 under high dilution conditions to form the corresponding amide cryptands 38 together with dimeric analogues 39 and some polymers. The compounds were easily separated by column chromatography on alumina and were fully characterised by mass spectrometry, elemental analysis, and multinuclear NMR... 

Poti, S. and Monlaudo, G., Analysis of Polymers by Mass Spectrometry, in Analysis of Polymers Systems, L. S. Bark and N. S. Allen, Eds. Applied Science, London, 1982. 

Leon, J. W. and Fr het, J. M. J., Analysis of Aromatic Polyether Dendrimers and Dendrimer-linear Block Copolymers by Matrix-assisted Laser Desorption Ionization Mass Spectrometry, Polym. Bull., 35, 449,1995. 

Lub, L, van Vroonhove, F.C.B.M., Bruninx, E., and Benninghoven, A., "Interaction of Nitrogen and Ammonia Plasmas with Polystyrene and Polycarbonate Studied by X-Ray Photoelectron-Spectroscopy, Neutron-Activation Analysis and Static Secondary Ion Mass-Spectrometry," Polymer 30, 40-44,1989. 

See also Activation Analysis Neutron Activation. Atomic Absorption Spectrometry Principles and Instrumentation. Atomic Emission Spectrometry Principles and Instrumentation. Chromatography Overview Principles. Gas Chromatography Pyrolysis Mass Spectrometry. Headspace Analysis Static Purge and Trap. Infrared Spectroscopy Near-Infrared Industrial Applications. Liquid Chromatography Normal Phase Reversed Phase Size-Exclusion. Microscopy Techniques Scanning Electron Microscopy. Polymers Natural Rubber Synthetic. Process Analysis Chromatography. Sample Dissolution for Elemental Analysis Dry... 

See MASS SPECTROMETRY Liquid Secondary Ion Mass Spectrometry. SURFACE ANALYSIS Secondary Ion Mass Spectrometry of Polymers... 

Bauer, B.I, Wallace, W.E., Fanconi, B.M., Guttman, C M. (2001) Covalent cationization method for the analysis of polyethylene by mass spectrometry. Polymer, 42,9949-9953. 

Leon, J. W., and Rrechet, J. M. 1995. Analysis of aromatic polyether dendrimers and dendrimer-hnear block copolymers by matrix-assisted laser desorption ionization mass spectrometry. Polym Bull 35(4), 449-455. 

Surface analysis has made enormous contributions to the field of adhesion science. It enabled investigators to probe fundamental aspects of adhesion such as the composition of anodic oxides on metals, the surface composition of polymers that have been pretreated by etching, the nature of reactions occurring at the interface between a primer and a substrate or between a primer and an adhesive, and the orientation of molecules adsorbed onto substrates. Surface analysis has also enabled adhesion scientists to determine the mechanisms responsible for failure of adhesive bonds, especially after exposure to aggressive environments. The objective of this chapter is to review the principals of surface analysis techniques including attenuated total reflection (ATR) and reflection-absorption (RAIR) infrared spectroscopy. X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and secondary ion mass spectrometry (SIMS) and to present examples of the application of each technique to important problems in adhesion science. 

Thermogravimetric analysis has also been used in conjunction with other techniques, such as differential thermal analysis (DTA), gas chromatography, and mass spectrometry, for the study and characterisation of complex materials such as clays, soils and polymers.35... 

Two relatively new techniques, matrix assisted laser desorption ionization-lime of flight mass spectrometry (MALDI-TOF) and electrospray ionization (FS1), offer new possibilities for analysis of polymers with molecular weights in the tens of thousands. PS molecular weights as high as 1.5 million have been determined by MALDI-TOF. Recent reviews on the application of these techniques to synthetic polymers include those by Ilantoif54 and Nielen.555 The methods have been much used to provide evidence for initiation and termination mechanisms in various forms of living and controlled radical polymerization.550 Some examples of the application of MALDI-TOF and ESI in end group determination are provided in Table 3.12. The table is not intended to be a comprehensive survey. 

Lecchi, P. and Abramson, E, Analysis of bio-polymers by size-exclusion chro-matography-mass spectrometry, /. Chromatogr. A, 828, 509, 1999. 

Selective extractions are not only of interest to solvent extraction, but also to thermal extractions. For example, selective in situ detection of polymer additives is possible using laser mass spectrometry, notably UV laser desorption/MS [561]. The proper matching of extraction technique to a sample determines the success of the operation and enhances the precision and accuracy of the analysis. 

Table 6.3 Mass spectrometry for polymer/additive analysis...

Applications Mass spectrometry has often been used more as an auxiliary, rather than a primary, identification method for additives in polymers. Table 6.5 shows the suitability of various ionisation modes for oligomer (and polymer) analysis. 

The mass spectra of mixtures are often too complex to be interpreted unambiguously, thus favouring the separation of the components of mixtures before examination by mass spectrometry. Nevertheless, direct polymer/additive mixture analysis has been reported [22,23], which is greatly aided by tandem MS. Coupling of mass spectrometry and a flowing liquid stream involves vaporisation and solvent stripping before introduction of the solute into an ion source for gas-phase ionisation (Section 1.33.2). Widespread LC-MS interfaces are thermospray (TSP), continuous-flow fast atom bombardment (CF-FAB), electrospray (ESP), etc. Also, supercritical fluids have been linked to mass spectrometry (SFE-MS, SFC-MS). A mass spectrometer may have more than one inlet (total inlet systems). 

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