NMR properties of poly(dimethyl siloxane) colloids as new contrast agents for NMR imaging

By connecting the field‐gradient spin‐echo theory to spin–spin relaxation, we have found that the relationship between the tube‐reptation model and spin–spin relaxation can be represented by G(t) = exp[−(t/T₂) ⁿ] in which n = 1 and 0.5 for regimes IV and III, respectively. In our experiments, the spin–spin relaxation of linear poly(dimethyl siloxane) (PDMS) agrees with G(t) = exp[−(t/T₂)] while that of crosslinked PDMS coincides with G(t) = exp[−(t/T₂)^0.5]. These results reflect that in the time interval 8–800 ms the dynamics of linear PDMS are in regime IV (governed by reptation motions) and those of the crosslinked PDMS are in regime III (dominated by wriggling motions). The line‐shapes of NMR spectra of crosslinked PDMS are consistent with the Lorentzian rather than the Gaussian model. This can be accounted for by supposing that the PDMS chains between crosslinks have liquid‐like motions even though crosslinked PDMS is a solid. The liquid‐like motions of crosslinked PDMS could be regarded as wriggling motions described by the tube‐reptation model. In addition, the experimental results of diameter distribution, viscosity, NMR image and spin–lattice relaxation are presented in this work. © 2000 Society of Chemical Industry     

An investigation of 1H and 13C longitudinal relaxation and relaxation in the rotating frame in solid poly(N‐vinylcarbazole)

¹H and ¹³C longitudinal relaxation times (T₁) and relaxation times in the rotating frame (T_1ρ) have been measured for poly(N‐vinylcarbazole) in the solid state in air and nitrogen atmospheres in an attempt to elucidate molecular motions. In air, the T₁ relaxation of both ¹H and ¹³C was dominated by interaction with absorbed paramagnetic oxygen. In nitrogen, the ¹³C T₁ relaxation times were long (>300 s) and were averaged by ¹³C–¹³C spin diffusion. The ¹³C T_1ρ relaxation times showed an exponential dependence on the strength of the rotating ¹³C magnetic field and were thus controlled by spin–spin processes rather than spin–lattice processes. © 2001 Society of Chemical Industry     

Reinforcement of poly(dimethylsiloxane) networks by montmorillonite platelets

A PDMS network, synthesized from a vinyl‐terminated precursor, was reinforced by plate‐like montmorillonite (volclay) particles with different surface cations. The optimal ratio of crosslinker‐to‐PDMS precursor was ascertained from the mechanical properties of networks prepared with different crosslinker concentrations. The elastic modulus of the polymer was enhanced by the montmorillonite particles. The increase in modulus was higher in the Li– than in the Na–volclay composites. The ultimate strength of the composites was also strongly enhanced by the small platelets, especially in presence of surface Li⁺. The stronger influence of Li–volclay on the mechanical properties of the composites can be attributed to the partial formation of an intercalated structure, which leads to thinner particles with a high aspect ratio. Both composite strength and modulus were proportional to the filler‐volume‐fraction, but the increase in strength was limited by rising particle agglomeration at high loading. In contrast to organic‐modified montmorillonite, the inorganic surface of volclay catalyzed the thermal degradation of PDMS. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2175–2183, 2002     

Dielectric and thermal studies of segmental dynamics in silica/PDMS and silica/titania/PDMS nanocomposites

Effects of silica and silica/titania nanoparticles on glass transition and segmental dynamics of poly(dimethylsiloxane) (PDMS) were studied for composites of a core–shell type using differential scanning calorimetry, thermally stimulated depolarization current, and dielectric relaxation spectroscopy techniques. Strong interactions between the filler and the polymer suppress crystallinity (T_c, X_c) and affect significantly the evolution of the glass transition in the nanocomposites. The segmental relaxation associated with the glass transition consists of three contributions, arising, in the order of decreasing mobility, from the bulk (unaffected) amorphous polymer fraction (α relaxation), from polymer chains restricted between condensed crystal regions (α_c relaxation), and from the semi‐bound polymers in an interfacial layer with strongly reduced mobility due to interactions with surface hydroxyls of silica and silica/titania nanoparticles (α′ relaxation). The evolution of surface affected CH₃ groups, as well as the degree of interaction of PDMS molecules with surface hydroxyl groups as a function of treatment temperature, was assessed by Fourier transform infrared spectroscopy, thermogravimetry and differential thermal analysis. The effectiveness of silica/PDMS and silica/titania/PDMS nanocomposites as hydrophobic coatings was investigated by static contact angle measurements. It was shown that the presence of titania nanoparticles and adsorbed PDMS promotes the hydrophobic properties of the PDMS coating after treatment in the 80–650°C range. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41154.     

NMR characterization of absorbed water in equilibrium swollen hydrogel P(AM‐NaA)

The behavior of absorbed water in equilibrium‐swollen poly(acrylamide‐co‐sodium acrylate) [P(Am‐NaA)] hydrogel is studied with ¹H nuclear magnetic resonance (¹H‐NMR). The observed non‐exponential decay of the spin–spin relaxation data manifests at least two distinguishable environmental states of the absorbed water in all samples. The component, characterized by the relatively shorter T₂, is associated with the more tightly bound water; whereas the other, characterized by longer T₂, might be a combination of near normal and loosely bound water. Attention is directed to the way in which relaxation times and the corresponding fraction of each type of water behave as a function of the crosslink density at 25°C. There is evidence of a sudden change of the crosslink state in P(Am‐NaA) hydrogel at crosslink density of about 1.0%. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1203–1207, 1999     

13C CP–MAS NMR study of absorbed water in polyimide film

Solid-state nuclear magnetic resonance (NMR) relaxation studies were performed on Kapton H polyimide films in order to determine the location of water absorption within the polymer lattice and its effects on the microdomain properties of the polymer. Carbon spin lattice relaxation (^13CT₁), spin lattice relaxation in the rotating frame (T_1ρ), and inversion recovery cross polarization (IRCP) experiments were performed to analyze wet and dry Kapton films and films exposed to D₂O. The conventional pulse sequences for these experiments were modified with a TOSS acquisition sequence in order to remove spinning side bands from the ¹³C-NMR spectra. The data indicates that the water molecules aggregate near the carbonyl group of the imide ring and are most probably bound via hydrogen bonding. Additionally the water molecules plasticize the polymer network by increasing the amplitude of low-frequency motions. © 1994 John Wiley & Sons, Inc.     

Effects of blending on the molecular dynamics of highly interacting binary polymer blends of poly(methyl methacrylate) and poly[styrene‐co‐(maleic anhydride)]

The molecular dynamics and miscibility of highly interacting binary polymer blends of poly(methyl methacrylate) (PMMA) and poly[styrene‐co‐(maleic anhydride)] random copolymer with 8 wt% maleic anhydride content (SMA) were investigated as a function of composition over a wide range of frequency (10^?2–10⁶ Hz) at different constant temperatures (30–160 °C). Only one common glass relaxation process (α‐process) was detected for all measured blends, and its dynamics and broadness were found to be composition dependent. The existence of only one common α‐relaxation process located at a temperature range between those of the pure polymer components indicated the miscibility of the two polymer components over the entire range of composition. The miscibility was also confirmed by measuring the glass transition temperatures of the blends, T_g, using differential scanning calorimetry. The composition dependence of T_g of the blends showed a positive deviation from the linear mixing rule and well described by the Gordon–Taylor–Kwei equation. The relaxation spectrum of the blends was resolved into α‐ and β‐relaxation processes using the Havriliake–Negami (HN) equation and ionic conductivity. The dielectric relaxation parameters obtained from HN analysis, such as broadness of relaxation processes, maximum frequency, f_max, and dielectric strength, Δ? (for the α‐ and β‐relaxation processes), were found to be blend composition dependent. The kinetics of the α‐relaxation process of the blends were well described by the Meander model, while an Arrhenius‐type equation was used to evaluate the molecular dynamics of the β‐relaxation process. Blending of PMMA and SMA was found to have a considerable effect on the kinetics and broadness of the β‐relaxation process of PMMA, indicating that the strong interaction and miscibility between the two polymer components could effectively change the local environment of each component in the blend. © 2013 Society of Chemical Industry     

Thermal and pulse NMR analysis of water in poly(2-hydroxyethyl methacrylate)

Hydrophilic three-dimensional methacrylate polymer networks (hydrogels) were prepared from 2-hydroxyethyl methacrylate (HEMA) monomer and tetraethylene glycol dimethacrylate (TEGDMA) as crosslinker. The nature and states of water in these hydrogels were studied by differential thermal analysis and pulse NMR relaxation spectroscopy. The thermal studies showed no endotherm peak for ice melting in the lower water content (bound water region); there are two endotherms peaks for higher water content hydrogels near 0°C. The amounts of bound water, intermediate water, and bulklike (free) water in the hydrogels were determined from a quantitative analysis of the endotherms of the water melting transitions. The water structure ordering in the hydrogels were discussed in terms of the fusion entropy and enthalpy obtained from the endotherm. Nuclear magnetic relaxation spectroscopy was also used to understand the mobilities of the water protons in the hydrogels and the interaction of water molecules with the gel networks. The measured spin-lattice relaxation time (T₁) values for water protons in the hydrogels are greatly reduced compared to that of liquid water. The measured values of spin–spin relaxation times (T₂) of water protons in the hydrogels are approximately 10 times less than that of T₁ and are almost constant in the region of bound water content. Beyond the bound water content region in the hydrogels, the T₂ values rapidly increase as the water content increases.     

High oxygen permeable Zeolite-4A poly(dimethylsiloxane) membrane for air separation

High oxygen permeability with optimal selectivity of the membrane is required for advancement in air separation membrane technology. Zeolite 4A-PDMS composite membranes were prepared by incorporation of Zeolite 4A nanoscale crystals during the polymerization process of PDMS membrane using toluene and n-heptane solvents, and their oxygen gas permeability and selectivity were explored. Small angle neutron scattering (SANS) technique was further used to study the polymer chain conformation and structure of membranes influenced by Zeolite 4A loading. The intersegmental distance between polymer chains and polymer chain aggregation or clustering were found to be increased on increasing the Zeolite 4A content in the membranes. Increment in the O₂ permeability and O₂/N₂ selectivity were observed for both type of membranes (toluene and n-heptane) with 1 wt% Zeolite 4A loading. The best performance result with O₂/N₂ selectivity of 2.6, and O₂ permeability of 1052 Barrer was exhibited by PDMS/toluene membrane loaded with 1 wt% Zeolite 4A. The PDMS/toluene membranes with 10 wt% Zeolite 4A loading exhibited increased O₂ permeability of 1245 Barrer with a fair O₂/N₂selectivity of ~1.7, while the PDMS/n-heptane membrane with the same loading exhibited excellent O₂ permeability of 6773 Barrer but lesser O₂/N₂ selectivity of ~1.2. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48047.     

Dynamic mechanical properties of three‐component composites (acrylic polymer/epoxy/SiO2) in the glass‐transition region

In previous studies, we reported the linear and nonlinear rheological properties of three‐component composites consisting of acrylic polymer (AP), epoxy resin (EP), and various SiO₂ contents (AP/EP/SiO₂) in the molten state. In this study, the dynamic mechanical properties of AP/EP/SiO₂ composites with different particle sizes (0.5 and 8 μm) were investigated in the glass‐transition region. The EP consisted of three kinds of EP components. The α relaxation due to the glass transition shifted to a higher temperature with an increase in the volume fraction (?) for the AP/EP/SiO₂ composites having a particle size of 0.5 μm, but the α relaxation scarcely shifted for the composite having a particle size of 8 μm as a general result. This result suggested that the SiO₂ nanoparticles that were 0.5 μm in size adsorbed a lot of the low‐glass‐transition‐temperature (T_g) component because of their large surface area. The AP/SiO₂ composites did not exhibit a shift in T_g; this indicated that the composite did not adsorb any component. The modulus in the glassy state (E′_g) exhibited a very weak &phis; dependence for the AP/EP/SiO₂ composites having particle sizes of 0.5 and 8 μm, although E′_g of the AP/SiO₂ composites increased with &phis;. The AP/EP/SiO₂ composites exhibited a peculiar dynamic mechanical behavior, although the AP/SiO₂ composites showed the behavior of general two‐component composites. Scanning electron microscopic observations indicated that some components in the EP were adsorbed on the surface of the SiO₂ particles. We concluded that the peculiar behavior of the AP/EP/SiO₂ composites was due to the selective adsorption of the EP component. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40409.     

Solid state 13C‐NMR study of a plasticized PLA/PHB polymer blend

High‐resolution solid‐state ¹³C nuclear magnetic resonance spectra and ¹³C spin–lattice relaxation times T₁(¹³C) are used to characterize the structure of a polymer blend prepared from poly(lactic acid) (85 wt %) and poly(3‐hydroxybutyrate) (15 wt %) and the effect of the plasticizer triacetine on the structure and molecular dynamics of the blend. Single‐pulse and cross‐polarization magic angle spinning ¹³C nuclear magnetic resonance spectra indicate that the nonplasticized polymer blend consists of semicrystalline poly(3‐hydroxybutyrate) domains built into an amorphous poly(lactic acid) matrix. Triacetine supports formation of the crystalline regions within both polymer components in the blend. Spin–lattice relaxation times of carbonyl carbons indicate that the nonplasticized polymer blend consists of noninteracting chains of blended polymers and plasticization of the polymer blend increases the relaxation rate. The glass transition, cold crystallization, and melting processes of the nonplasticized and plasticized blends were also studied using differential scanning calorimetry methods. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46296.     

Some dynamic mechanical properties of unimodal and bimodal networks of poly(dimethylsiloxane)

Summary Elastomeric networks of polydimethylsiloxane prepared by end-linking chains having molecular weights in the range 18,500 to 220 g mol^-1 were studied from -128 to 50°C using a Rheovibron DDV III Viscoelastometer. In the case of the unimodal networks, the glass transition temperature T_g was generally insensitive to degree of cross-linking. The intensity of the tan δ relaxation, however, increased by over an order of magnitude over the range of cross-link densities investigated. Bimodal networks prepared from mixtures of relatively long and very short PDMS chains also had values of T_g which were insensitive to degree of cross-linking. Finally, as expected, the intensities of the tan δ peak for the bimodal networks could not be explained on the basis of simple additivity of contributions from the relatively long and the very short network chains.     

Morphology of poly(styrene‐block‐dimethylsiloxane) copolymer films

The morphologies of poly(styrene‐block‐di‐methylsiloxane) (PS‐b‐PDMS) copolymer thin films were analyzed via atomic force microscopy and transition electron microscopy (TEM). The asymmetric copolymer thin films spin‐cast from toluene onto mica presented meshlike structures, which were different from the spherical structures from TEM measurements. The annealing temperature affected the surface morphology of the PS‐b‐PDMS copolymer thin films; the polydimethylsiloxane (PDMS) phases at the surface were increased when the annealing temperature was higher than the PDMS glass‐transition temperature. The morphologies of the PS‐b‐PDMS copolymer thin films were different from solvent to solvent; for thin films spin‐cast from toluene, the polystyrene (PS) phase appeared as pits in the PDMS matrix, whereas the thin films spin‐cast from cyclohexane solutions exhibited an islandlike structure and small, separated PS phases as protrusions over the macroscopically flat surface. The microphase structure of the PS‐b‐PDMS copolymer thin films was also strongly influenced by the different substrates; for an asymmetric block copolymer thin film, the PDMS and PS phases on a silicon substrate presented a lamellar structure parallel to the surface at intervals. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1010–1018, 2007     

Macroporous poly(dicyclopentadiene) beads

Macroporous poly(dicyclopentadiene) beads have been produced via chemically induced phase separation in suspension polymerization. Phase separation is promoted by the enthalpic and entropic changes induced by the polymerization of dicyclopentadiene. By using poly(1,2‐butylene glycol) monobutyl ether (M_n 500 g/mol), which is not soluble in the suspending medium, as the porogen, the stabilized droplets of the monomer/porogen mixture can be considered microreactors in which both polymerization and phase separation occur, resulting in solid, biphasic microspheres. The porogen is then extracted with methanol and the particles are finally dried. The resulting macroporous crosslinked poly(dicyclopentadiene) beads are analyzed by scanning electron microscopy, mercury intrusion porosimetry, and nitrogen adsorption and are compared with similar bulk samples. Materials containing isolated pores as well as microstructures built with agglomerated particles have been produced. The porous microspheres showed micrometric average pores' access diameters and specific surface areas ranging from 1.3 to 3.1 m²/g. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 407–415, 2005     

Phase transformations of some poly(vinyl alcohol)–NiCl2 composites

Samples of poly(vinyl alcohol)–NiCl₂ composites containing up to 30 wt% NiCl₂ were prepared by casting in order to study phase transformation–structural change relationships of these samples before and after heat treatment. Differential thermal analysis (DTA) thermograms were recorded at 10, 15, 20 and 30 °C min^?1. For untreated samples four endotherms were assigned as: rotation of hydroxyl groups in the glassy state, glass transition, structural transition in the rubber‐like state, and melting transition. Ultrasonic attenuation measurements were carried out to confirm these transitions in the glassy and rubber‐like states. In the glassy state, the effect of NiCl₂ addition is explained in terms of chain stiffness due to the creation of local crosslinked regions in amorphous parts of the polymer. Average values of activation energies for glass transition were calculated using both methods of Kissinger and Ozawa. However, addition of NiCl₂ had an opposite effect on the heating rate independent crystallization melting temperature (T_m), relative to that on T_g. The DTA thermograms of heat‐treated samples indicated that square planar NiCl₂ molecules were embedded in the polymer matrix with no local crosslinking role due to the formation of conjugated polyenes along the polymer chains by thermal treatment. Copyright © 2003 Society of Chemical Industry     

Reactive blending of poly (dimethylsiloxane) with nylon 6 and poly (styrene):Effect of reactivity on morphology

Reactive compatibilization was used to control and stabilize 20–30wt% poly(dimethylsioxane) (PDMS) dispersions in nylon 6 (PA) and poly(styrene) (PS), respectively. The effect of the type of reation (amine (NH₂)/anhydride (An), NH₂/ epoxy(E) and carboxylic acid (COOH)/E) on the morphology was studied with electron microscopy. PS and PDMS have mutual solvents thus it was possible to use gel permeation chromatography (GPC) to determine the concentration of block copolymer in PS/PDMS blends. Reactive blending of PA6 with difunctional PDMS‐(AN)₂ did not decrease the PDMS particle size compared to the non‐reactive blend (～10μm). Particle size decreaeased significantly to about 0.5 μm when PA6 was blended with a PDMS containing about 4 random An groups along the chain. For the PS/PDMS blends, GPC revealed that the NH₂/An reaction formed about 3% block copolymer and produced stable PDMS particles ～ 0.4 μm. No reaction was detected for the PS‐NH₂/PDMS‐E blend and the morphology was coarse and unstable. Also, PS‐NH₂/PDMS‐An reactivity was lower compared to other systems such as PS/ poly (isoprene) and PS/poly(methaacrylte) using the same reaction. This was attributed to the relatively thinner PS/PDMS interface dueto the high PS/PDMs immiscibility.     

Stress relaxation of polyisoprene–laponite nanocomposites monitored by magic angle spinning 1H NMR and optical microscopy

In order to illustrate the capacity of nuclear magnetic resonance (NMR) to monitor compression‐induced changes in the morphology of nanocomposites, solid‐state NMR results were directly contrasted with optical microscopy. Increases in the interfacial area of Laponite clay in cis 1,4‐polyisoprene composites were monitored during uniaxial compression. Interaction of the Co⁺² in the clay galleries with the polymer decreases the polymer's ¹H spin‐lattice relaxation time constant (T₁). The composite showed a decrease in T₁ time constant with increasing compressive strain. This behavior is consistent with an increase in interfacial area of the aggregate as it breaks apart. Increases in interfacial area of the aggregate were confirmed with optical micrographs. POLYM. COMPOS., 26:799–805, 2005. © 2005 Society of Plastics Engineers     

Effect of annealing on poly(urethane‐siloxane) copolymers

Poly(urethane‐siloxane) copolymers were prepared by copolymerization of OH‐terminated polydimethylsiloxane (PDMS), which was utilized as the soft segment, as well as 4,4′‐diphenylmethane diisocyanate (MDI) and 1,4‐butanediol (1,4‐BD), which were both hard segments. These copolymers exhibited almost complete phase separation between soft and hard segments, giving rise to a very simple material structure in this investigation. The thermal behavior of the amorphous hard segment of the copolymer with 62.3% hard‐segment content was examined by differential scanning calorimetry (DSC). Both the T₁ temperature and the magnitude of the T₁ endotherm increased linearly with the logarithmic annealing time at an annealing temperature of 100°C. The typical enthalpy of relaxation was attributed to the physical aging of the amorphous hard segment. The T₁ endotherm shifted to high temperature until it merged with the T₂ endotherm as the annealing temperature increased. Following annealing at 170°C for various periods, the DSC curves presented two endothermic regions. The first endotherm assigned as T₂ was the result of the enthalpy relaxation of the hard segment. The second endothermic peak (T₃) was caused by the hard‐segment crystal. The exothermic curves at an annealing temperature of above 150°C exhibited an exotherm caused by the T₃ microcrystalline growth. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5174–5183, 2006     

Studies of polymer mobility in composite blends of poly(vinyl butyral) and alumina

Solid-state NMR and thermal analysis techniques were used to compare the mobility of poly(vinyl butyral) (PVB) in the presence and absence of both alumina filler particles and plasticizer. The relative mobility of main-chain and side-chain carbons increases in the presence of both plasticizer and alumina as seen from an increase in the average cross-polarization rates, 〈T_CH〉, and from a general decrease in the rotating frame spin-lattice relaxation rates, ^CT_1ρ. Unlike the main-chain carbons, inversion recovery cross-polarization (IRCP) data on solution cast composites show that the side-chain methyl groups in neat PVB samples are best characterized by a monoexponential cross-polarization model. However, in the presence of alumina, a fraction of the methyl groups becomes less mobile as indicated by the biexponential IRCP behavior. Polymer phase mobility also increases below the critical pigment volume concentration (CPVC) as seen from decreasing transition temperatures using dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). This is accompanied by an increase in the rigidity of a portion of the polymer phase above the CPVC as indicated by an increase in the apparent T_g, along with an increase in the mobility of another portion as indicated by the appearance of a low-temperature DMA transition. These trends are consistent with an increase in polymer chain packing heterogeneity in the presence of alumina. © 1993 John Wiley & Sons, Inc.     

Synthesis and characterization of poly(ester ether siloxane)s

A series of novel thermoplastic elastomers based on ABA‐type triblock prepolymers, poly[(propylene oxide)–(dimethylsiloxane)–(propylene oxide)] (PPO‐PDMS‐PPO), as the soft segments, and poly(butylene terephthalate) (PBT), as the hard segments, was synthesized by catalyzed two‐step melt transesterification of dimethyl terephthalate (DMT) with 1,4‐butanediol (BD) and α,ω‐dihydroxy‐(PPO‐PDMS‐PPO) (M?_n = 2930 g mol^?1). Several copolymers with a content of hard PBT segments between 40 and 60 mass% and a constant length of the soft PPO‐PDMS‐PPO segments were prepared. The siloxane‐containing triblock prepolymer with hydrophilic terminal PPO blocks was used to improve the compatibility between the polar comonomers, i.e. DMT and BD, and the non‐polar PDMS segments. The structure and composition of the copolymers were examined using ¹H NMR spectroscopy, while the effectiveness of the incorporation of α,ω‐dihydroxy‐(PPO‐PDMS‐PPO) prepolymer into the copolyester chains was controlled by chloroform extraction. The effect of the structure and composition of the copolymers on the transition temperatures (T_m and T_g) and the thermal and thermo‐oxidative degradation stability, as well as on the degree of crystallinity, and some rheological properties, were studied. Copyright © 2006 Society of Chemical Industry