Stereoregularity and polymerization mechanism of polymethacrylonitriles determined by 13C-NMR spectroscopy

Carbon-13 nuclear magnetic resonance (¹³C-NMR) spectra of polymethacrylonitriles prepared under various conditions were measured. In acetone solution, the α-methyl carbon absorptions were split into triads and partially into pentads, and the methylene carbon absorptions into tetrads. In trifluoroacetic acid solution, the α-methyl carbon absorptions were split into pentads and the cyano carbon absorptions into triads. The triad, tetrad, and pentad tacticities determined from ¹³C-NMR spectra were compared with dyad tacticities determined from proton NMR spectra. The stereoregularity of the polymers which are γ-ray-initiated in liquid phase at temperatures near melting point (?35.8°C) and in the solid state differs from that of the polymers radically initiated at ?20 to 80°C. The stereoregularity and the conversion suggest the existence of an ionic mechanism in the polymerization at low temperatures.     

Wideline NMR studies of polyacrylonitrile

NMR linewidth studies of molecular motion in several polyacrylonitrile samples have been carried out. The motional transition temperature is found in the 105–124°C. range and depends upon polymerization conditions. In addition, the thermal activation energy for the motional process underlying this transition was evaluated at 16.4 kcal./mole. Finally, measurement of the transition temperature for one of the specimens in three different physical states (bulk, spun only, and spun and drawn with a ratio of 3:1), revealed that no change in the transition temperature was effected by either spinning or drawing.     

Stereoregularity of poly(2-vinylpyridine) determined by 1H-NMR and 13C-NMR spectroscopy

In order to determine the stereoregularity of poly(2-vinylpyridine), 2-vinylpyridine-β,β-d₂ was synthesized. The ¹H-NMR spectra of the deuterated polymer in D₂SO₄ and o-dichlorobenzene solutions showed three peaks, which were assigned to triad tacticities. Since the absorptions of heterotactic and syndiotactic triads of methine protons overlap those of methylene protons in nondeuterated polymers, only isotactic triad intensities can be obtained from the ¹H-NMR spectra of nondeuterated poly(2-vinylpyridine). The ¹³C-NMR spectra of poly(2-vinylpyridine) were obtained in methanol and sulfuric acid solutions. In methanol solution the absorption was split into three groups, which cannot be explained by triads, and in sulfuric acid solution several peaks were observed. These splittings may be due to pentad tacticity. The results show that poly(2-vinylpyridine) obtained by radical polymerization is an atactic polymer.     

Observation of pentads in deuterated polyacrylonitrile by NMR spectroscopy

The deuterium-decoupled methine proton spectra of polyacrylonitrile-β,β-d₂ were measured at 156°C in dimethylsulfoxide-d₆ solution. Splittings of triad peaks caused by pentad sequences were observed. The isotactic triad resonance was resolved into three peaks and the heterotactic resonance into two peaks, while the syndiotactic resonance was unresolved or resolved into three peaks. The splittings were assigned by comparing the probability of each pentad sequence with observed intensities. The pentad signal shifted to the higher magnetic field with increasing number of meso configurations as neighbors of the central triad. It was observed that the pentad of atactic polyacrylonitrile-β,β-d₂ obeyed Bernoullian statistics but that of isotactic polymer obtained by γ-ray irradiation of the canal complex seemingly obeyed first-order Markov statistics.     

The phases of polymers as determined by NMR

Nuclear magnetic resonance (NMR) spectroscopy has been used to study the morphology and dynamics in semicrystalline polymers. Dynamics may be observed through NMR relaxation rates that are sensitive to motions in the 1–10⁸ Hz range, or through modulation of anisotropic magnetic interactions, such as the chemical shift and dipole-dipole interactions. Morphological structure may be inferred through NMR measurements of polymer dynamics or investigated directly through studies of the magnetic interactions. Here, we discuss the study of morphological structure in semicrystalline polymers using NMR, and review results on poly(ethylene terephthalate) that address the question of the number of phases in this semicrystalline polymer.This work was funded by the Office of Naval Research.     

Stereoregularity of poly(α-methylvinyl alkyl ether)s determined by 1H- and 13C-NMR spectroscopy

α-Methylvinyl methyl ether, ethyl ether, and isobutyl ether were polymerized under various polymerization conditions and the structure of the polymers was determined by ¹H- and ¹³C-NMR spectroscopy. α-Methyl and β-methylene carbon spectra of poly(α-methylvinyl isobutyl ether) showed splitting and were analyzed by triad and tetrad sequences. β-Methylene carbon spectra of poly(α-methylvinyl ethyl ether) also showed splitting. When Eu(fod)₃ was added, α-methyl and methoxy proton spectra in benzene of poly(α-methylvinyl methyl ether) showed splitting assigned to triad tacticities. All the polymers obtained in polar solvents exhibited an increase in syndiotacticity. The polymerization mechanism is discussed.     

Local protein backbone folds determined by calculated NMR chemical shifts

NMR chemical shifts (CSs: δN(NH), δC(α), δC(β), δC', δH(NH), and δH(α)) were computed for the amino acid backbone conformers (α(L), β(L), γ(L), δ(L), ε(L), α(D), γ(D), δ(D), and ε(D) [Perczel et al., J Am Chem Soc 1991, 113, 6256]) modeled by oligoalanine structures. Topological differences of the extended fold were investigated on single β-strands, hairpins with type I and II β-turns, as well as double- and triple-stranded β-sheet models. The so-called "capping effect" was analyzed: residues at the termini of a homoconformer sequence unit usually have different CSs than the central residues of an adequately long homoconformer model. In heteroconformer sequences capping effect ruins the direct applicability of several chemical shift types (δH(NH), δC', and δN(NH)) for backbone structure determination of the parent residue. Experimental δH(α), δC(α), and δC(β) values retrieved from protein database are in good agreement with the relevant computed data in the case of the common backbone conformers (α(L), β(L), γ(L), and ε(L)), even though neighboring residue effects were not accounted for. Experimental and computed ΔδH(α)-ΔδC(α), ΔδH(α)-ΔδC(β), and ΔδC(α)-ΔδC(β) maps give qualitatively the same picture, that is, the positions of the backbone conformers relative to each other are very similar. This indicates that the H(α), C(α), and C(β) chemical shifts of alanine depend considerably on the backbone fold of the parent residue also in proteins. We provide tabulated CSs of the chiral amino acids that may predict the various structures of the residues.     

Effective size and fractal dimension of polyelectrolytes determined by diffusion NMR

Polyelectrolytes are macromolecules containing dissociable or charged groups on the main chain or in side groups. These charges are the basis of the water solubility of polyelectrolytes. The solution properties namely the conformation is determined by an interplay of thermodynamic and electric interactions. The electrostatic interaction is influenced by the ionic strength of the solution. As a measure of the effective size of the macromolecules the hydrodynamic radius is determined from the self-diffusion coefficient measured via pulsed- field gradient nuclear magnetic resonance. From variation of the hydrodynamic radius with molecular weight for each ionic strength, the fractal dimension has been determined for the example of poly(styrenesulfonate). With increasing ionic strength the fractal dimension, which describes the use of space for the fictitious growth of the molecule when increasing the molecular weight, increases. This implies a denser packing of the molecules in higher ionic strength.     

Molecular probe location in reverse micelles determined by NMR dipolar interactions

The location and interactions of solutes in microheterogeneous environments, such as reverse micelles, critically influence understanding of many phenomena that utilize probe molecules to characterize properties in chemical, biological, and physical systems. The information gained in such studies depends substantially on the location of the probe used. Often, intuition leads to the assumption that ionic probe molecules reside in the polar water pool of a system. In this work, the location of a charged polar transition metal coordination complex in a reverse micellar system is determined using NMR spectroscopy. Despite the expected Coulomb repulsion between the surfactant headgroups and the negatively charged complex, the complex spends significant time penetrating into the hydrophobic portion of the reverse micellar interface. These results challenge the assumption that ionic probe molecules reside solvated by water in microheterogeneous environments and suggest that probe molecule location be carefully considered before interpreting data from similar systems.     

NMR and x-ray studies on the morphology of thermoreversible polyacrylonitrile gels

The morphology of thermoreversible polyacrylonitrile–propylene carbonate (PAN-PC) gels was examined using solid-state carbon-13 nuclear magnetic resonance (NMR) spectroscopy and x-ray diffraction. Following complete dissolution of the polymer at elevated temperature and cooling of the concentrated PAN-PC solutions, a gel was formed. The PAN-PC gels consisted of regions of mobile polymer chains, rich in PC, “cross-linked” by regions of rigid polymer. The mobile regions of the gels showed solution-type NMR spectra with resolution of tacticity effects. The rigid component detected by NMR would correspond to the crysttallites detected previously by x-ray diffraction. Wide-angle x-ray diffractograms of the gels showed different peaks when compared with the dry polymer powder. After solvent extraction and drying of the gel, the diffractogram reverted to that of the original dry powder. This new result is the strongest evidence to support the view advanced earlier that the new peaks found in the diffraction pattern of the wet gels arises from solvated polymer crystallites rather than from ordinary polymer crystallites. © 1993 John Wiley & Sons, Inc.     

Water-protein and ligand-protein interactions as determined by selective NMR relaxation studies

Water-macromolecules and ligand-macromolecules interactions were investigated considering the effects induced by the presence of a macromolecule on both the water and the ligand NMR selective (R₁^SE) and non-selective (R₁^NS) spin-lattice relaxation rates. The results obtained from the solvent studies were used to describe the solvent dynamics at the macromolecule-solvent interface. On the other hand, ligand R₁^SE and (R₁^NS) analysis allowed the definition of the “affinity index”, [A]_L^T, an index related to the extent of the macromolecule-ligand recognition process.     

Studies on the tacticity of polyacrylonitrile. III. NMR spectra of stereoisomers of 2,4,6-tricyanoheptane as model compounds of polyacrylonitrile

The three stereoisomers of 2,4,6-tricyanoheptane were separated and their NMR spectra were studied as the three-unit model compounds of polyacrylonitrile. The chemical shifts and coupling constants obtained from the NMR spectra were compared to those of the two-units model compounds. The geminal protons for the isotactic methylene are not equivalent, but the difference of the chemical shifts is smaller than that in the meso two-unit model. The racemic methylene signals appear at higher field than the meso methylene in the heterotactic three-unit model as in the case of the racemic and the meso two-unit models. The signals of the methinic protons in triads appear in the order: isotactic CH, heterotactic CH, and syndiotactic CH from the high field. From the observed values of the vicinal coupling constants, the chain conformations of the model compounds are also discussed.     

Microstructure of silica monolayer solid acid catalysts determined by 29Si NMR spectroscopy

The nuclear magnetic resonance (NMR) of ²⁹Si showed that the silica monolayer, which was prepared by chemical vapor deposition (CVD) of Si(OCH₃)₄ at 593 K on alumina, mainly consisted of Si(OAl)₁(OSi)₃ and Si(OAl)₁(OSi)₂(OH)₁ species, in agreement with the mechanism of formation of monolayer. The Brønsted acid site is suggested to be the latter species. On the other hand, such an isolated species as Si(OAl)₃(OH)₁ was formed from Si(OCH₃)(CH₃)₃. Lack of acidity on this species indicates that the acidity requires the siloxane network.     

Dynamics of silica-supported catalysts determined by combining solid-state NMR spectroscopy and DFT calculations

The molecular dynamics of a series of organometallic complexes covalently bound to amorphous silica surfaces is determined experimentally using solid-state nuclear magnetic resonance (NMR) spectroscopy and density functional theory calculations (DFT). The determination is carried out for a series of alkylidene-based catalysts having the general formula [([triple bond]SiO)M(ER)(=CH(t)Bu)(R')] (M = Re, Ta, Mo or W; ER = C(t)Bu, NAr or CH2(t)Bu; R' = CH2(t)Bu, NPh2, NC4H4). Proton-carbon dipolar coupling constants and carbon chemical shift anisotropies (CSA) are determined experimentally by solid-state NMR. Room-temperature molecular dynamics is quantified through order parameters determined from the experimental data. For the chemical shift anisotropy data, we validate and use a method that integrates static values for the CSA obtained computationally by DFT, obviating the need for low-temperature measurements. Comparison of the room-temperature data with the calculations shows that the widths of the calculated static limit dipolar couplings and CSAs are always greater than the experimentally determined values, providing a clear indication of motional averaging on the NMR time scale. Moreover, the dynamics are found to be significantly different within the series of molecular complexes, with order parameters ranging from = 0.5 for [([triple bond]SiO)Ta(=CH(t)Bu)(CH2(t)Bu)2] and [([triple bond]SiO)Re([triple bond]C(t)Bu)(=CH(t)Bu)(CH2(t)Bu)] to = 0.9 for [([triple bond]SiO)Mo([triple bond]NAr)(=CH(t)Bu)(R') with R' = CH2(t)Bu, NPh2, NC4H4. The data also show that the motion is not isotropic and could be either a jump between two sites or more likely restricted librational motion. The dynamics are discussed in terms of the molecular structure of the surface organometallic complexes, and the orientation of the CSAs tensor at the alkylidene carbon is shown to be directly related to the magnitude of the alpha-alkylidene CH agostic interation.     

Dynamic processes and chemical composition of Lepidium sativum seeds determined by means of field-cycling NMR relaxometry and NMR spectroscopy

Proton nuclear magnetic resonance (NMR) techniques, such as field-cycling relaxometry, wide-line NMR spectroscopy, and magic angle spinning NMR spectroscopy, were applied to study the seeds of cress, Lepidium sativum. Field-cycling NMR relaxometry was used for the first time to investigate the properties of the whole molecular system of dry cress seeds. This method not only allowed the dynamics to be studied, but was also successful in the differentiation among the solid (i.e., carbohydrates, proteins, or fats forming a solid form of lipids) and liquid-like (oil compounds) components of the seeds. The ¹H NMR relaxation dispersion of oils was interpreted as a superposition of intramolecular and intermolecular contributions. The intramolecular part was described in terms of a Lorentzian spectral density function, whereas a log–Gaussian distribution of correlation times was applied for the intermolecular dipole–dipole contribution. The models applied led to very good agreement with the experimental data and demonstrate that the contribution of the intermolecular relaxation to the overall relaxation should not be disregarded, especially at low frequencies. A power-law frequency dependence of the proton relaxation dispersion was used for the interpretation of the solid components. From the analysis of the ¹H wide-line NMR spectra of the liquid-like component of hydrated cress seeds, we can conclude that the contribution of oil protons should always be taken into account when evaluating the spin–lattice relaxation times values or measuring the moisture and oil content. The application of ¹H magic angle spinning NMR significantly improves resolution in the liquid-like spectrum of seeds and allows the determination of the chemical composition of cress seeds.

Stereoregularity of poly(methyl acrylate)

The stereoregularity of poly(methyl acrylate) and poly(methyl acrylate-αd) was determined from the NMR spectra. A method of quantitative determination of stereoregularity of poly(methyl acrylate) proposed in this paper is based on the fact that in the 100 Mc./sec. NMR spectrum the absorption peaks due to methylene protons in syndiotactic configurations overlap absorptions due to only one of two methylene protons in isotactic configurations. The stereostructure of poly(methy1 acrylates) polymerized with anionic catalysts such as Grignard reagents, n-butyllithium, and LiAlH₄ is generally richer in isotactic diads than in syndiotactic diads. For example, poly(methyl acrylate) polymerized with phenylmagnesium bromide as catalyst at ?20°C. consists of 99% isotactic and 1% syndiotactic diads. In radical polymerization, the isotacticity of poly(methyl acrylate) is independent of polymerization temperature. Poly(methyl acrylates) polymerized with a Ziegler-Natta catalyst consisting of Al(C₂H₅)₂Cl and VCl₄ have configurations similar to those polymerized by radical initiators. The stereoregularity of poly(methyl acrylate-α-d) resembled that of poly(methyl acrylate) polymerized under the same conditions.     

Stereoregularity of poly(vinyl ether)

α-Methylvinyl isobutyl and methyl ethers were polymerized cationically and the structure of the polymers was studied by NMR. Poly(α-methylvinyl methyl ether) polymerized with iodine or ferric chloride as catalyst was found to be almost atactic, whereas poly(α-methylvinyl isobutyl ether) polymerized in toluene with BF₃OEt₂ or AlEt₂Cl as catalyst was found to be isotactic. In both cases, the addition of polar solvent resulted in the increase of syndiotactic structure as is the case with polymerization of alkyl vinyl ether. tert-Butyl vinyl ether was polymerized, and the polymer was converted into poly(vinyl acetate), the structure of which was studied by NMR. A nearly linear relationship between the optical density ratio D₇₂₂/D₇₃₆ in poly(tert-butyl vinyl ether) and the isotacticity of the converted poly(vinyl acetate) was observed.     

Stereoregularity of Poly(methyl Methacrylate) Obtained by New Complex Bases

The stereoregularity of poly(methyl methacrylate) obtained with complex bases in various solvents was determined by ¹H-NMR spectroscopy. Polymethyl methacrylates produced by complex bases are mostly hetero and/or syndiotactic and obey Bernoullian statistics.