Nuclear magnetic resonance diene polymers

Infrared spectroscopy has been used for quantitatively measuring the amounts of 1,2-, 3,4-, cis-1,4-, and trans-1,4-polymers in the polymerization of 1,3-dienes its use for analysis of isotactic and syndiotactic polymer structures is very limited [Coleman et al., 1978 Tosi and Ciampelli, 1973]. Nuclear magnetic resonance spectroscopy is the most powerful tool for detecting both types of stereoisomerism in polymers. High-resolution proton NMR and especially 13C NMR allow one to obtain considerable detail about the sequence distribution of stereoisomeric units within the polymer chain [Bovey, 1972, 1982 Bovey and Mirau, 1996 Tonelli, 1989 Zambelli and Gatti, 1978],... 

Isomerism in diene polymers can be measured by infrared and nuclear magnetic resonance spectroscopy. Some of the polymerization methods described in Chapter 9 allow the production of polydienes with known controlled constitutions and geometrical configurations. 

An in-depth characterization of the coupling product by nuclear magnetic resonance (NMR) and mass spectrometry (MS) revealed the preferential insertion of two diene units in the middle of the polymer backbone, mainly following a trons-1,4-addition pathway characteristic of a radical process [60]. Based on these observations, and also on additional density functional theory (DPT) calculations, a three-step mechanism was proposed for CMRC (Figure 4.4) ... 

Schaefer et al. (19) studied the interphase microstructure of ternary polymer composites consisting of polypropylene, ethylene-propylene-diene-terpolymer (EPDM), and different types of inorganic fillers (e.g., kaolin clay and barium sulfate). They used extraction and dynamic mechanical methods to relate the thickness of absorbed polymer coatings on filler particles to mechanical properties. The extraction of composite samples with xylene solvent for prolonged periods of time indicated that the bound polymer around filler particles increased from 3 to 12 nm thick between kaolin to barium sulfate filler types. Solid-state Nuclear Magnetic Resonance (NMR) analyses of the bound polymer layers indicated that EPDM was the main constituent adsorbed to the filler particles. Without doubt, the existence of an interphase microstructure was shown to exist and have a rather sizable thickness. They proceeded to use this interphase model to fit a modified van der Poel equation to compute the storage modulus G (T) and loss modulus G"(T) properties. 

The properties of some polymers are dependent on their microstructure for example isotactic polypropylene is crystalline whereas atactic polypropylene is amorphous. Microstructure effects are also exemplified by polybutadienes, where the mode of addition of the diene to the growing chain leads to 1,2-addition, 1,3-addition and 1,4-addition, which may be as or trans. The fraction of different addition species changes the mechanical properties of the polymer. Another example is provided by the chemical composition of a copolymer and its sequence distribution, which together determine its ultimate properties. It is thus of great importance to be able to characterize polymer micro structure. This is generally done using spectroscopic methods, specifically infrared spectroscopy and nuclear magnetic resonance spectroscopy. 

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