NMR Approach to the kinetics of polymer crystallization. II. Polydimethylsiloxane solutions

The dilution effect on the crystallization kinetics of PDMS/toluene solutions, ranging from a polymer volume fraction of ? = 1.00 (pure PDMS) to ? = 0.32, was studied using ¹H high-power NMR. Spin-spin magnetic response was analyzed into relaxation components, arising from the different phases of the semicrystalline sample, through a spin-echo technique. The intensity and shape of the amorphous component provide relevant information concerning (1) the global crystallization process and (2) the state of hindrance of the amorphous chains induced by the growing crystalline domains. It was shown that, in solutions, the main effect on the crystallization kinetics of changing concentration is to depress the equilibrium melting temperature of the system. However, a radically distinct crystallization rate between the pure and the more concentrated system must be explained in terms of the activation energy for interphase chain transport. Thermodynamic parameters of PDMS crystallites were also deduced from a model. Comparison between the isothermal development of the overall crystallinity and the variation of a characteristic relaxation time of the amorphous PDMS proton response gives an insight into the relative predominance of nucleation or growth rates in the crystallization mechanisms.     

Carbon-13 NMR studies of local dynamics in polymer solutions and melts

Carbon-13 spin-lattice relaxation time measurements have been performed at two experimental frequencies on a series of amorphous polymers in the bulk state at temperatures well above the glass-transition temperatures and in solution. The high experimental values of the T₁ minimum as a function of temperature cannot be accounted for only by the specific orientation autocorrelation functions developed for polymers. They indicate the existence of an additional fast anisotropic motion, which we have assigned to librations of limited but significant extent of the internuclear CH vectors about their rest position. Moreover, in most cases, the temperature dependence of the segmental motions proves that they are involved in the glass-rubber transition phenomena.     

NMR studies of polymer solutions. III. Conformational transition study of oligomeric polyethylene in mixed solvents

The intramolecular structure of oligomeric polyethylene (PE) in solvent mixtures of α-chloronaphthalene and carbon tetrachloride, α-chloronaphthalene and deuterated octane, and α-chloronaphthalene and deuterated hexadecane was studied at 35°C. by a high-resolution nuclear magnetic resonance technique. It was clearly shown that the n-alkanes show no detectable selective solvent absorption in these systems. The conformational structure (P_p), which was formed in “bulky” aromatic solvents when the chain length was greater than 16, was significantly destroyed by the presence of carbon tetrachloride, octane, or hexadecane in the above-mentioned solvent mixtures. Therefore, the “bulky” aromatic solvents, such as α-chloronaphthalene and 9-chloroanthracene, can be classified as P_p-structure-promoting solvents, in which the PE remains in the P_p conformation. In contrast, carbon tetrachloride and linear alkanes are P_m-structure-promoting solvents, in which the PE does not exhibit any P_p structure but is in the disordered P_m conformation. It is speculated that the P_p structure is caused by a “chain-fold” mechanism.     

Silicon-29 NMR studies of aqueous silicate solutions: Part II. Isotopic enrichment

Silicon-29 NMR spectra have been recorded for aqueous solutions of sodium silicate in the alkaline pH range using silica enriched in the ²⁹Si isotope. Work at low concentration shows that essentially only monomeric orthosilicate ions are present at ca. 0.01 M in silica. At higher concentrations, peaks which lack fine structure indicate species whose silicon nuclei are all equivalent. The experiments have assisted in the difficult process of assigning the spectra of silicate solutions.     

PFG NMR studies of lysine-silica solutions

The formation process of silica nanoparticles in lysine-silica mixtures was studied using dynamic light scattering (DLS) and pulsed-field gradient (PFG) NMR measurements. (1)H NMR shows line broadening of the lysine resonances during TEOS hydrolysis/nanoparticle formation. Analysis of the TEOS hydrolysis kinetics show that TEOS hydrolysis is the rate-limiting step in particle formation, and has an activation energy of 20.5 kJ/mol. Transverse relaxation measurements show a corresponding decrease in T(2) with TEOS hydrolysis, indicating a reduction in the lysine mobility due to lysine-silica interactions. PFG NMR results indicate a systemic decrease in the self-diffusion coefficient of lysine as particle formation proceeds. The results obtained can be described using a two-state model wherein lysine is either free in solution or bound to the nanoparticles. Analysis of the PFG data of samples made at various temperatures show that lysine coverage upon complete hydrolysis is between 2.5 and 2.8 mmol lysine/kg solution, and insensitive to the heating temperature. PFG NMR shows a linear increase in the amount of bound lysine with increasing lysine content, indicating an increase in the surface area present, i.e. more and smaller particles, with increased lysine content. The PFG NMR results presented give quantitative insights that indicate that while pH is likely the primary driver for the rate of particle formation and particle size, lysine is critical for stabilization of the nanoparticles.     

Spin-probe studies. II. Applications to polymer characterization

The spin-probe technique has been employed to study interactions between several small organic nitroxides and host polymers in which they are dissolved. By this method one is able to study the mobility of the dissolved molecule in its microscopic environment using electron spin resonance spectroscopy. The behavior of one nitroxide has been examined in twelve different polymers and copolymers. An ESR line shape parameter has been correlated with T_m and T_g. In addition, energy barriers for the rotation of the dissolved nitroxides in the polymers have been calculated. They range from 7.8 to 18 kcal/mole, depending on the structure of the nitroxide and the polymer. Similar experiments in a hydrocarbon solvent afford a rotational energy barrier of 3.8 kcal/mole.     

Electrophoretic NMR studies of polymer and surfactant systems

The aim of this tutorial review is to introduce to a broader readership the emerging technique of electrophoretic NMR (eNMR). The "electrophoretic" element of the technique refers to the fact that charged particles are induced to flow by the application of an electric field. This flow is measured using pulsed-gradient spin-echo NMR (PGSE-NMR). The great potential of this experimental approach is the fact that NMR is chemically selective and non-invasive. eNMR, especially when combined with the more established PGSE-NMR experiment, may therefore be used to quantify the structure of multi-component systems via the dynamics and charge of each species within a complex mixture. Accordingly, eNMR is likely to be of great significance for colloid scientists, biologists, technologists and formulation scientists.     

Adiabatic compressibility of polymer solutions—II. Polystyrene in toluene

Adiabatic compressibility data for polystyrene, using samples of various molecular weights dissolved in toluene, are reported as a function of concentration. These data are compared with calculations of the incremental compressibility obtained from viscoelastic and longitudinal acoustic relaxation studies. The differences between the observed and calculated increments are attributed to polymer-solvent interactions.     

Solvent self-diffusion,polymer NMR relaxation,and free volume in polymer solutions

The self-diffusion coefficient of chloroform in poly(isopropyl acrylate)—chloroform solutions has been studied as a function of concentration and temperature by using the pulsed-field-gradient spin-echo NMR method. It is found that the self-diffusion coefficient of the solvent can be adequately fitted by using a simple free-volume approach with either a concentration or temperature superposition. It was noted that the free-volume parameters derived from the self-diffusion data are the same as those derived from deuterium NMR transverse relaxation-time measurements of the polymer in the same system. The equality of these two sets of experiments suggests a fundamental relationship between the two different processes. The simplest explanation is that the free volume necessary for the local segmental motion of the polymer and the translation of the solvent are similar.     

29Si NMR studies of zeolite precursor solutions

Solution 29Si NMR spectroscopy results of zeolite precursor solutions of composition 1 SiO2:4 C2H5OH:0.36/n R+n[OH-]n:20 H2O are reported. This work employs isotopically enriched 29Si materials to aid in spectral interpretation. Using both 1D and 2D methods, spectra of solutions containing tetrapropylammonium hydroxide are wholly consistent with the existing silicate chemistry literature and indicate that the majority of the species are high-symmetry silicate clusters previously observed in aqueous solutions. The results are inconsistent with the nanoblock or nanoslab model proposed by Kirschhock and co-workers. Mixtures containing the 4,4'-trimethylene-bis(1,1'-dimethylpiperidinium) dihydroxide cation were also studied. These mixtures have similar speciation to the TPA solutions, although the relative populations of the species are different. Preliminary variable temperature 29Si NMR of these mixtures shows that the exchange properties of the high-symmetry silicate species, most notably the tetrahedral tetramer, depend on the organocation identity.     

Surface tension of polymer solutions. II. Poly-isobutylenes in n-heptane and tetralin

The surface tensions of solutions of polyisobutylene fluids in n-heptane and tetralin have been measured at room temperature. The polyisobutylene samples studied range in molecular weight from 400 to 2800. The results conform closely to the predictions of equations previously developed from a simplified lattice theory calculation.     

Solid-state NMR studies of pharmaceutical solids in polymer matrices

Biodegradable drug-delivery systems can be formulated to release drug for hours to years and have been used for the controlled release of medications in animals and humans. An important consideration in developing a drug-delivery matrix is knowledge of the long-term stability of the form of the drug and matrix after formulation and any changes that might occur to the drug throughout the delivery process. Solid-state NMR spectroscopy is an effective technique for studying the state of both the drug and the matrix. Two systems that have been studied using solid-state NMR spectroscopy are presented. The first system studied involved bupivacaine, a local anesthetic compound, which was incorporated into microspheres composed of tristearin and encapsulated using a solid protein matrix. Solid-state ¹³C NMR spectroscopy was used to investigate the solid forms of bupivacaine in their bulk form or as incorporated into the tristearin/protein matrix. Bupivacaine free base and bupivacaine-HCl have very different solid-state NMR spectra, indicating that the molecules of these compounds pack in different crystal forms. In the tristearin matrix, the drug form could be determined at levels as low as 1:100 (w/w), and the form of bupivacaine was identified upon loading into the tristearin/protein matrix. In the second case, the possibility of using solid-state ¹³C NMR spectroscopy to characterize biomolecules lyophilized within polymer matrices is evaluated by studying uniformly ¹³C-labeled asparagine (Asn) in 1:250 (w/w) formulations with poly(vinyl pyrrolidone) (PVP) and poly(vinyl alcohol) (PVA). This work shows the capability of solid-state NMR spectroscopy to study interactions between the amino acid and the polymer matrix for synthetic peptides and peptidomimetics containing selective ¹³C labeling at the Asn residue.     

Corresponding state relations for the Newtonian viscosity of polymer solutions. II. Further systems and concentrated solutions

In earlier work we have indicated a superposition principle for moderately concentrated mixtures (c ? 2/[η]) in good and poor solvents. By an examination of data on a number of vinyl polymers and cellulose derivatives in good as well as poor solvents, the validity of this principle is extended to concentrated solutions (c ? 50%). The characteristic concentration factor γ is proportional to M over the whole concentration range, with 0.47 ≤ a₁ ≤ 1.10 being larger for good than for poor solvents, the result obtained earlier. Significant deviations from this relationship are noted in good solvents for those low molecular weights at which deviations from the usual intrinsic viscosity relationship occur. This may be related to the expansion factor of the polymer coil. On the basis of these results, the concentration and molecular weight dependence of the viscosity in the concentrated solution can be related to each other in terms of the parameter a₁ and thus to thermodynamic characteristics. In this manner a bridge between the relatively dilute and concentrated regions is established. Currently used semiempirical expressions are analyzed in terms of these results. For the polystyrene–cyclohexane systems and θ ? 9 ≦ T ≦ θ + 3, γ can be identified with the critical concentration for phase separation. Provided an “entanglement” concentration c_e exists, in the neighbourhood of which the concentration dependence of the viscosity changes reapidly, γ can alternatively be shown to be proportional to c_e, or c_e ∝ M. The temperature reduction scheme suggested earlier remains to be investigated.     

NMR investigations of phase transition in aqueous polymer solutions and gels

The use of NMR spectroscopy in investigations of phase transitions in aqueous polymer solutions and gels is reviewed. Results on this subject as obtained mostly for thermoresponsive polymers (e.g., poly(N-isopropylacrylamide) and its copolymers, poly(N-isopropylmethacrylamide) and its copolymers, poly(vinyl methyl ether)) from temperature dependences of ¹H and ¹³C NMR spectra, spin–lattice and spin–spin relaxation times, diffusion coefficients and NMR images are discussed.     

Ion and polymer dynamics in polymer electrolytes PPO-LiClO4. II. 2H and 7Li NMR stimulated-echo experiments

We use 2H NMR stimulated-echo spectroscopy to measure two-time correlation functions characterizing the polymer segmental motion in polymer electrolytes PPO-LiClO4 near the glass transition temperature Tg. To investigate effects of the salt on the polymer dynamics, we compare results for different ether oxygen to lithium ratios, namely, 6:1, 15:1, 30:1, and infinity. For all compositions, we find nonexponential correlation functions, which can be described by a Kohlrausch function. The mean correlation times show quantitatively that an increase of the salt concentration results in a strong slowing down of the segmental motion. Consistently, for the high 6:1 salt concentration, a high apparent activation energy Ea=4.1 eV characterizes the temperature dependence of the mean correlation times at Tg相似文献   

Nuclear magnetic resonance studies of polymer solutions. I. Poly(methyl methacrylates)

The microscopic interactions of solvent with the diastereoisomeric units of isotactic and syndiotactic poly(methyl methacrylate) have been studied by high-resolution nuclear magnetic resonance. The changes in chemical shifts in various solvents were compared with those of low molecular weight analogs, methyl acetate, and methyl propionate. These changes are caused mainly by the ring-current effect, which has been found to be larger for the low molecular weight analogs than for the polymer. This is especially true when the protons on the polymer backbone are compared with the corresponding ones in the low molecular weight compounds. As one changes from a chloroform solvent to an aromatic solvent, the displacements of the chemical shifts of the polymer can be expressed as percentages of the corresponding shifts of methyl acetate. For syndiotactic poly(methyl methacrylate) in chlorobenzene, benzene, and α-chloronaphthalene, respectively, the percentages are 82, 93, 75 for ester protons; 35, 29, 17 for the backbone methylene protons; and 18, 6.7, 0 for the backbone α-methyl protons. For isotactic poly(methyl methacrylate) in chlorobenzene and benzene, respectively, the percentages are 71, 76 for the ester protons; 41, 38 for the backbone methylene protons; and 41, 32 for the backbone α-methyl protons. These results are discussed in terms of the local stereochemistry of the polymer systems. The exploitation of procedures of this sort in revealing details of polymer behavior in solution indicates dramatic possibilities for future investigations.     

Molecular dynamics and NMR studies of proteins in ionic solutions

The molecular dynamics of water and selected ions was studied in concentrated electrolyte solutions with, or without, proteins added. Our experimental results by multinuclear spin relaxation techniques were then compared with molecular dynamics computations for water and ions in concentrated electrolyte solutions. The mechanisms for the anionic and cationic interactions with myofibrillar proteins in aqueous solutions were investigated by nuclear magnetic resonance over a wide range of salt concentrations. The multinuclear spin relaxation data were analyzed with a thermodynamic linkage model of hydrated ion clusters of various sizes and composition. Protein amide groups were found to bind to anions with strengths in the order of the lyotropic series.     

Crystallization characteristics of polymer blends. I. Polyethylene and polystyrene

Blends of polyethylene and polystyrene have been prepared to study the effect of the morphology on their crystallization characteristics since the polymers are known to phase separate. The polymer component present in least amount formed a dispersed phase of discrete spherical particles whose number and size altered with blend composition. However, close to 50% composition cylindrical rods of polyethylene dispersed in polystyrene were observed. With polyethylene in excess the kinetics of crystallization were insensitive to the morphology, but with polyethylene present as the dispersed phase they became dependent on the size and number of the spheres, and in particular on the nucleation density. When the number of spherical particles exceeded that of heterogeneous nuclei, larger supercoolings, and so presumably homogeneous nucleation, were required for crystallization to develop further. The degree of crystallization of the blends then became dependent on the temperature of crystallization rather than on time, and the isothermal crystallization appearing to be instantaneous.