Polymer blends deuterated components

They demonstrated the surface eiuichment of the star in isotopic blend with a linear polystyrene counterpart by dynamic secondary ion mass spectroscopy. However, in this study the star polymer was the deuterated component and had a lower molar mass than the linear matrix. Therefore, one could question if these two factors aren t themselves driving the surface segregation. 

Nuclear magnetic resonance (NMR) has been applied to the study of homogeneity in miscible polymer blends and has been reviewed by Cheng [11a] and Roland [11b]. When the components of a blend have different Tg s, proton NMR can be used to assess the phase structure of the blend by taking advantage of the rapid decrease of proton-proton coupling with nuclear separation [lie]. For blends containing elastomers of almost identical Tg, proton MAS NMR is applied to blends where one of the components is almost completely deuterated [12], Another technique is crosspolarization MAS NMR [13], The transfer of spin polarization from protons to the atoms of... 

Renewed interest in polymer blends has provoked a re-examination of the scattering laws for multicomponent systems, not only with a view to obtaining thermodynamic parameters, but also to assess the possibilities of removing the interference from the other components. This question has been particularly addressed by Jahshan and Summerfield and Koberstein they show that for a two phase system containing a proportion of deuterated material, essentially a three component polymer, then Eq. (14) should be written as ... 

As N 00, Xc 0 and the chains become immiscible at all temperatures (see Figure 31.9). The entropy of mixing polymers is so small that ev en an extremely small unfavorable enthalpy of mixing can prevent mixing. For example, even deuterated polybutadiene will not mix with protonated polybutadiene below a critical temperature of 61.5 °C, if N = 2300. Rather than mix, polymer blends often separate into domains of each of the component polymers. 

We have used forward recoil spectrometry to measure the mutual diffusion and tracer diffusion coefficients, D and D, in the miscible polymer blend of deuterated polystyrene (d-PS) poly(xylenyl ether) (PXE). Using the fast theory of mutual diffusion, D is related to the D, degree of polymerization N, and volume fraction of the individual blend components by,... 

In the solid, dynamics occurring within the kHz frequency scale can be examined by line-shape analysis of 2H or 13C (or 15N) NMR spectra by respective quadrupolar and CSA interactions, isotropic peaks16,59-62 or dipolar couplings based on dipolar chemical shift correlation experiments.63-65 In the former, tyrosine or phenylalanine dynamics of Leu-enkephalin are examined at frequencies of 103-104 Hz by 2H NMR of deuterated samples and at 1.3 x 102 Hz by 13C CPMAS, respectively.60-62 In the latter, dipolar interactions between the 1H-1H and 1H-13C (or 3H-15N) pairs are determined by a 2D-MAS SLF technique such as wide-line separation (WISE)63 and dipolar chemical shift separation (DIP-SHIFT)64,65 or Lee-Goldburg CP (LGCP) NMR,66 respectively. In the WISE experiment, the XH wide-line spectrum of the blend polymers consists of a rather featureless superposition of components with different dipolar widths which can be separated in the second frequency dimension and related to structural units according to their 13C chemical shifts.63... 

In this case study, which is extracted from reference 184, infrared dichroism is described as a means of separating the component dynamics in multicomponent polymer melts. What is necessary is the existence of distinct absorption peaks for at least one of the components. In the present problem, however, where two chains of identical chemistry but different molecular weights are mixed, there will not be any intrinsic differences in their absorption spectra. In this case it is necessary to label one of chains with a tag that will allow its presence in the blend to be revealed. For this purpose, deuteration of one of the chains is often used. This provides the labeled chain with an absorption of infrared light at the symmetric stretching vibration of the C-D bond, which occurs in the vicinity of 2180 cm-1. Fortunately, the unlabeled polymer contains no absorption peak at this location. It is important, however, to determine that the presence of a label on one species will not alter the physical response of the sample at a level that will affect the phenomena under study. For example, the labeling should not induce phase separation or cause unwanted specific interactions. 

Practical problems associated with infrared dichroism measurements include the requirement of a band absorbance lower than 0.7 in the general case, in order to use the Beer-Lambert law in addition infrared bands should be sufficently well assigned and free of overlap with other bands. The specificity of infrared absorption bands to particular chemical functional groups makes infrared dichroism especially attractive for a detailed study of submolecular orientations of materials such as polymers. For instance, information on the orientation of both crystalline and amorphous phases in semicrystalline polymers may be obtained if absorption bands specific of each phase can be found. Polarized infrared spectroscopy can also yield detailed information on the orientational behavior of each component of a pol3mier blend or of the different chemical sequences of a copoljnner. Infrar dichroism studies do not require any chain labelling but owing to the mass dependence of the vibrational frequency, pronounced shifts result upon isotopic substitution. It is therefore possible to study binary mixtures of deuterated and normal polymers as well as isotopically-labelled block copolymers and thus obtain information simultaneously on the two t3q>es of units. 

In the above, we have seen that a certain interpolymer interaction is required for different polymers to be miscible. Here, we will see that high resolution NMR enables us to locate interacting regions in component polymers. One of the most useful methods is the nuclear Overhauser effect (NOE) between H— H and H—NOE can be observed between spins whose distances are less than about 0.5 nm. The one- (ID) and two-dimensional (2D) NOE experiments have been used to reveal the spatial structure of biomolecules in solutions. Of course, these can be applied to locate interacting regions in a blend in solution and in solids [3]. For example, Crowther et al. [22] and Mirau et al. [23] applied NOE experiments to polystyrene/poly(vinyl methyl ether) (PS/PVME) in a toluene solution, and show that the interpolymer NOE signals between the aromatic protons of PS and the methoxy protons of PVME can be observed at polymer concentrations higher than 25 wt%. In the solid state, Heffner and Mirau [24] measured 2D H— H NOESY (NOESY nuclear Overhauser effect spectroscopy) spectra of 1,2-polybutadi-ene and polyisoprene (1,2-PB/PI) and observed NOE cross-peaks between these component polymers. White and Mirau observed interpolymer NOE interactions between the H spins of PVME and the spins of deuterated... 

A special simplification arises when a deuterated polymer is blended with its hydrogenous counterpart of exactly the same molecular weight. In this case, the interference component of the scattered intensity turns out to be simply proportional to the independent scattering component, and as a result the form factor can be determined even when the concentration of the deuterated polymer is not dilute. This will be discussed more when the technique of deuterium labeling is described in Section 6.3. 

When the system of study is binary to begin with, for example, a polymer dissolved in a solvent or a blend of two polymers, the practice of deuterating one of the components... 

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