Fourier-transform infrared spectroscopy block copolymers

By sequential copolymerization of styrene and propylene using a modified Ziegler-Natta catalyst, MgCl2/TiCl4/NdClc(OR) //Al(iBu)3, which was developed in our laboratory, a styrene-propylene block copolymer is obtained. After fractionation by successive solvent extraction with suitable solvents, the copolymer was subjected to extensive molecular and morphological characterization using 13C-NMR, DSC, DMTA, and TEM. The results indicate that the copolymer is a crystalline diblock copolymer of iPS and iPP (iPS-fo-iPP). The diblock copolymer contains 40% iPS as determined by Fourier transform infrared spectroscopy and elemental analysis. 

Heischer et al. [172] measured the interfacial tension reductirai credited to the complexation between carboxy-terminated PBD and amine-terminated PDMS, which were added to an immiscible blend of PBD and PDMS. The changes in interfacial tensimi resembled the behavior observed for block copolymer addition to homopolymer blends there is initially a linear decrease in interfacial tension with the concentration of functional homopolymer up to a critical concentration, at which the interfacial tension becomes invariant to further increases in the concentration of functional material. However, the formation of interpolymer complexes depends on the equilibrium between associated and dissociated functional groups and, thus, the ultimate plateau value for interfacial tension reduction is dependent on the functional group stoichiometry. A reaction model for end-complexation was developed in order to reproduce the interfacial tension reduction data with Fourier transform infrared spectroscopy applied to determine the appropriate rate constants. The model provided a reasonable qualitative description of the interfacial tension results, but was not able to quantitatively predict the critical compositions observed experimentally. 

Block copolymerization of PCL and PPEs can be performed with the initiation of Al(0 Pr)3. In a typical example, the polymerization of s-CL was initiated by A3 in THF, followed by the addition of phosphoester monomer (eqn [3]). The actual formation of the expected block copolymers was confirmed by nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR), and gel permeation chromatography (GPC). Kinetic studies revealed that the of PPE follows a linear relationship with monomer conversion (up to 94.3%), and the molecular weight distribution remains narrow with dispersity (PDI) around 1.2, indicating that a limited amount of inter- or intramolecular transesterification reactions occurred. This enables the synthesis of block copolymers with narrow molecular weight distribution, controlled molecular weights, and adjustable compositions. 

Multiple block copolymers form a domain-matrix morphology due to the chemical and steric incompatibilities of the two chemically different blocks. The surface molecular and morphological structures of a series of block copolyether-urethane-ureas have been studied in detail via Electron Spectroscopy for Chemical Analysis (ESCA) and Fourier Transform Infrared Spectroscopy (FTIR) coupled with internal reflectance techniques. ESCA provides elemental information concerning the very surface, while FTIR provides the molecular and secondary bonding Information of the surface and into the bulk. Bulk and surface chemical and morphological structures are shown to be quite different, and are affected by synthetic and fabrication variables. 

No.24,23rd Nov.l992,p.6621-30 FOURIER TRANSFORM INFRARED AND ELECTRON SPECTROSCOPY FOR CHEMICAL ANALYSIS STUDIES OF BLOCK COPOLYMERS OF STYRENE AND DIMETHYLSILOXANE Chen X Gardella J A Kumler P L Buffalo,State University of New York New York,State University... 

The difficulty results, in part, from the fact that only a small fraction of the chemical bonds, generally less than one in a thousand, are involved in me-chanochemical processes. The concentration of connecting units is therefore at the detection limit and below for traditional analytical methods such as conventional nuclear magnetic resonance and infrared spectroscopy. The sensitivity can, of course, be enhanced by techniques such as cumulative, multiple scans, Fourier transform analysis, and difference techniques for detection to one part in ten thousand and better. It may yet be difficult to determine whether polymers are linked by chemical bonds or whether they are simply intimate mixtures. For this distinction, other tests can be of value. For example, the difference between blocks and blends for ethylene-propylene polymer systems has been distinguished by thermal analysis [5]. In many cases, simple extraction tests can distinguish between copolymers and blends. For example, for rubber milled into polystyrene, the fraction of extractable rubber is a measure of mechanochemistry. Conversely, only the rubber in this system is readily cross-linked by benzoyl peroxide after which free polystyrene may be conveniently extracted [6]. In another case, homopolymers of styrene and methyl methacrylate can be separated cleanly from each other and from their copolymers by fractional precipitation [7]. The success of such processes, of course, depends on both the compositions and molecular weights involved. 

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