PVP-LiCl-DMF溶液体系的流变学特性及相互作用

利用流变学方法, 采用核磁共振和红外光谱技术开展了聚乙烯吡咯烷酮(PVP)和LiCl相互作用研究, PVP/LiCl/DMF浓溶液的表观粘度随着LiCl含量的增加而提高, 溶液的粘流活化能也相应增加. 13C NMR结果表明, 溶液中Li+与PVP的羰基之间存在相互作用, 这种相互作用改变了PVP分子的聚集状态. 红外光谱结果证实了PVP/LiCl复合物中Li+与PVP的羰基存在相互作用.     

Poly(acrylonitrile) ultrafiltration membranes. I. Polymer‐salt‐solvent interactions

Fourier transform infrared spectroscopy was used to study the interactions among LiCl, ZnCl₂, and AlCl₃ with N,N‐dimethylformamide (DMF) and poly(acrylonitrile) (PAN). It was observed that all three salts complex with DMF as well as PAN. The strength of the cation interaction with the >C?O oxygen of DMF was found to be higher than that with the ? CN group of PAN. The >C?O stretching frequency of DMF with ZnCl₂ was red shifted, indicating stronger complex formation compared with other two cations. With the addition of salt, the salt–DMF pseudo solvent was found to become a θ solvent for PAN compared with neat DMF. This change in PAN solvation power was primarily the result of DMF–salt complexation. As a result of the complexation, Mark‐Houwink constant a, was found to reduce from 0.75 (for pure DMF) to ～0.6 for DMF–salt solvents, indicating decreased PAN chain expansion. Comparison of intrinsic viscosity [η] values indicated that addition of salts to PAN–DMF solutions resulted in: (i) decrease in the DMF solvation power, which causes less expanded polymer coils, and (ii) increased interpolymer chain entanglements via salt‐promoted chain association. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2061–2073, 2005     

Effect of the polymer matrix on the formation of silver nanoparticles in polymer–silver salt complex membranes

When polymer–silver salt complex membranes were exposed to UV irradiation, the separation performances of both the permeance and selectivity for propylene–propane decreased, which was primarily attributed to the reduction of the silver ions in the membranes to silver nanoparticles. Here, the effect of the polymer matrix on the formation of silver nanoparticles in the polymer–silver salt complex membranes was investigated. This effect was assessed for the complexes of two kinds of silver salts (AgBF₄ and AgCF₃SO₃) with several polymeric ligands containing three different carbonyl groups, including poly(vinyl pyrrolidone) (PVP) with an amide group, poly(vinyl methyl ketone) (PVMK) with a ketone group, and poly(methyl methacrylate) (PMMA) with an ester group. UV–vis spectra and transmission electron microscopy (TEM) images clearly indicated that the reduction rate of the silver ions has the following order in the various polymer matrices: PVP > PVMK > PMMA, whereas the size and the distribution of the nanoparticles exhibited the reverse order. The tendency to form silver nanoparticles was explained in terms of the differences between the comparative strengths of the interactions of the silver ions with the different carbonyl oxygens in the matrices, as well as that of the silver ions with counteranions, which was characterized by X‐ray photoelectron spectroscopy (XPS) and FT‐Raman spectroscopy. It was concluded that when the concentration of free silver ions was low due to weak polymer–silver ion and strong silver ion–anion interactions, as found with PMMA, the reduction rate of silver ions to silver nanoparticles was slow. Therefore, the PMMA–silver complex membranes were less sensitive to decreases in separation performance upon UV irradiation than compared to the PVP membranes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1168–1178, 2006     

Resistive‐type humidity sensors based on PVP–Co and PVP–I2 complexes

Poly(vinylpyrrolidone) films containing cobalt chloride or iodine were investigated to obtain information on their possible use as a humidity sensor element. FTIR and UV‐VIS spectroscopies were used to characterize the PVP–I₂ and PVP–Co complexes. Infrared spectroscopy revealed a structural change of both shape and intensity of the carbonyl and lactam bands, indicating the formation of an ion‐coordination polymer. The J–E curves for pure PVP, PVP–I₂, and PVP–Co films obey ohm's law at low voltages, deviate from the linear response at higher voltages, and finally display breakdown behavior. An increase in current density of the PVP matrix with iodine or cobalt doping is attributed to the formation of charge transfer complexes. The observed hysteresis of the I–V characteristics implies that there was some standing voltage in the film, which could be attributed to a disorientation of polar side groups of PVP. The electrical conductivities of the polymeric complexes were very sensitive to environmental humidity. An explanation of the humidity‐sensing behavior of the PVP–I₂ and PVP–Co complexes is presented. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 459–469, 2001     

Molecular modeling simulation and experimental measurements to characterize chitosan and poly(vinyl pyrrolidone) blend interactions

Blends of chitosan and poly(vinyl pyrrolidone) (PVP) have a high potential for use in various biomedical applications and in advanced drug‐delivery systems. Recently, the physical and chemical properties of these blends have been extensively characterized. However, the molecular interaction between these two polymers is not fully understood. In this study, the intermolecular interaction between chitosan and PVP was experimentally investigated using ¹³C cross‐polarization magic angle‐spinning nuclear magnetic resonance (¹³C CP/MAS NMR) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). According to these experimental results, the interaction between the polymers takes place through the carbonyl group of PVP and either the OH? C₆, OH? C₃, or NH? C₂ of chitosan. In an attempt to identify the interacting groups of these polymers, molecular modeling simulation was performed. Molecular simulation was able to clarify that the hydrogen atom of OH? C₆ of chitosan was the most favorable site to form hydrogen bonding with the oxygen atom of C?O of PVP, followed by that of OH? C₃, whereas that of NH? C₂ was the weakest proton donor group. The nitrogen atom of PVP was not involved in the intermolecular interaction between these polymers. Furthermore, the interactions between these polymers are higher when PVP concentrations are lower, and interactions decrease with increasing amounts of PVP. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1258–1264, 2008     

Influence of solvents on the formation of ultrathin uniform poly(vinyl pyrrolidone) nanofibers with electrospinning

Although there have been many reports on the preparation and applications of various polymer nanofibers with the electrospinning technique, the understanding of synthetic parameters in electrospinning remains limited. In this article, we investigate experimentally the influence of solvents on the morphology of the poly(vinyl pyrrolidone) (PVP) micro/nanofibers prepared by electrospinning PVP solution in different solvents, including ethanol, dichloromethane (MC) and N,N‐dimethylformamide (DMF). Using 4 wt % PVP solutions, the PVP fibers prepared from MC and DMF solvents had a shape like a bead‐on‐a‐string. In contrast, smooth PVP nanofibers were obtained with ethanol as a solvent although the size distribution of the fibers was somewhat broadened. In an effort to prepare PVP nanofibers with small diameters and narrow size distributions, we developed a strategy of using mixed solvents. The experimental results showed that when the ratio of DMF to ethanol was 50:50 (w/w), regular cylindrical PVP nanofibers with a diameter of 20 nm were successfully prepared. The formation of these thinnest nanofibers could be attributed to the combined effects of ethanol and DMF solvents that optimize the solution viscosity and charge density of the polymer jet. In addition, an interesting helical‐shaped fiber was obtained from 20 wt % PVP solution in a 50:50 (w/w) mixed ethanol/DMF solvent. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3721–3726, 2004     

Fluorescence,ion binding,and viscosity properties of poly[2‐ and 4‐vinylpyridine]s in methanol and in sulfuric acid

Fluorescence intensities of poly(2‐vinylpyridine) (P2VP) and poly(4‐vinylpyridine) (P4VP) in H₂SO₄/H₂O solutions were increased with increasing acid concentration. The intensities for P2VP were found to be six times stronger than that of P4VP. These differences were accounted for by the microenvironment of protonated pyridinium group. The ion binding properties of 4‐methylpyridine (4MP), P2VP, and P4VP were investigated in methanol using Tb³⁺ as a fluorescence probe. The increase of fluorescence intensity of Tb³⁺ in [P2VP–Tb³⁺] and [P4VP–Tb³⁺] complexes is due to both the replacement of the inner coordinated methanol molecules and ligand‐to‐metal energy transfer. The model compound 4MP was inefficient from this point of view, and the results were attributed to the polymer cooperative effect. Reduced viscosities of poly(vinylpyridine)s (PVP) in methanol were similar to nonionic polymers; however, when TbCl₃ was added into the solution, the viscosities increased upon dilution. These results also indicated that PVP form complexes with Tb³⁺ in methanol. When diluted, the counterions Cl⁻ are allowed to dissociate and the charged polymer expands. Consequently, the solution's viscosity increases. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1341–1345, 1999     

Hydrophobically modified poly(vinyl alcohol) using alkoxy‐substituted methyl gallate: Synthesis and rheology

Hydrophobically modified poly(vinyl alcohol) (HMPVA) polymers were synthesized by potassium t‐butoxide‐catalyzed reaction of PVA with methyl 3,4,5‐tris(n‐octyloxy) benzoate (MGC₈)/3,4,5‐tris(n‐dodecyloxy) benzoate (MGC₁₂) and 1,3‐propane sultone. The concentration of 1,3‐propane sultone was kept constant at 10 mol % and that of MGC₈ (2, 3, and 4 mol %)/MGC₁₂ (2 and 3 mol %) was varied to obtain HMPVAs with different hydrophobic contents. The incorporation of MGC₈/MGC₁₂ and 1,3‐propane sultone onto HMPVA was confirmed by NMR spectroscopy. Rheological properties of aqueous solutions also confirmed the presence of hydrophobic and charged functional groups on HMPVAs. In the semidilute regime, the specific viscosity of HMPVAs followed concentration scaling that is typical of polyelectrolytes. At higher concentrations, the HMPVA solutions with 3 and 4 mol % of MGC₈ exhibited large increase in specific viscosity. Oscillatory experiments on these solutions exhibited gel‐like behavior at polymer concentrations of 40–50 g/L. Confocal microscopy images of HMPVA with 4 mol % of MGC₈ clearly indicated the existence of microgels. The tendency of formation of microgels further increased with increasing chain length of the hydrophobe, that is, with MGC₁₂. These samples exhibited rheological behavior that is typical of soft solids and was therefore probed by the strain‐rate frequency superposition technique reported recently in the literature. HMPVAs with improved rheological properties show potential applications as thickeners in cosmetic creams, lotions and as drug carriers in pharmaceutical formulations. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1054–1063, 2010     

Effect of metal nature on energy of specific adsorption of chloride ions from dimethyl formamide solutions

The specific adsorption of chloride ions on the renewable liquid (Cd–Ga) electrode from mixed [0.1_m М LiCl + 0.1(1–_m) М LiBF₄] solutions in dimethyl formamide (DMF) is studied with an ac bridge at the following fractions of surface-active anion m: 0, 0.01, 0.02, 0.05, 0.1, 0.2, 0.5 and 1. It is found that the data on the specific adsorption of Cl^– anion in the system can be quantitatively described by Frumkin’s isotherm. The free adsorption energy of Cl^– (ΔG _ads) is a quadratic function of electrode charge. The results are compared with the corresponding data for the Ga/DMF and (In–Ga)/DMF interfaces. It is shown that the adsorption energy of Cl–anions at the metal/DMF interface depends on the metal nature and increases in the series (In–Ga) ≈ (Cd–Ga) < Ga. The energy of metal–DMF chemisorption interaction, which hampers ion adsorption, increases in the same series. The analysis of the data uniquely indicates that the free energy of metal–Cl^– interaction (ΔG _M-CL-) increases in the series (In–Ga) ≈ (Cd–Ga) < Ga. Thus, in the series of electrodes studied, the variations in the energies of metal–Cl^– and metal–DMF specific interaction are correlated: the higher the energy of metal–DMF chemisorption interaction, the higher the energy of metal interaction with Cl^–.     

Quaternary ammonium ion dendrimers from methylation of poly(propylene imine)s

The poly(propylene imine) dendrimers DAB‐dendr‐(NH₂)₈, DAB‐dendr‐(NH₂)₃₂, and DAB‐dendr‐(NH₂)₆₄ were fully converted with iodomethane to quaternary ammonium ions at both chain ends and branch points and, with less iodomethane, were partially converted to quaternary ammonium ions mainly at end groups. Amidation of the primary amine ends followed by treatment with iodomethane gave the first dendrimers with quaternary ammonium ions only at branch points. After an exchange of iodide counterions for chloride, all of the quaternary ammonium ion dendrimers slightly increased the rate of decarboxylation of 6‐nitrobenzisoxazole‐3‐carboxylate ion in an aqueous solution. Similar quaternary ammonium ion dendrimers with more hydrophobic interiors or more hydrophobic chains on the ends were much more active catalysts for the decarboxylation. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 821–832, 2001     

Studies on the equilibrium among poly(sodium 4‐styrenesulfonate), Cu2+, and iminodiacetic acid by ultrafiltration at constant ionic strength

The ultrafiltration technique evaluates the interactions of water‐soluble polymers with metal ions. Aqueous solutions containing poly(sodium 4‐styrenesulfonate) (PSS), Cu(NO₃)₂, NaNO₃, and iminodiacetic acid (IDAA) are examined by this technique. Cu²⁺ undergoes complex formation with IDAA and intreracts electrostatically with PSS. On the other hand, Na⁺ ions are in competition with Cu²⁺ for the electrostatic binding to PSS. The solutions are ultrafiltered keeping the ionic strength constant, so their compositions are allowed to change continuously. The concentration of Cu²⁺ bound to the polymer showed an exponential decay during filtration. The concentration of Cu²⁺ bound to the polymer before ultrafiltration is calculated by extrapolation. The concentration of the different species in solution is proposed as a function of the filtration factor. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2587–2593, 2002     

Vibrational Spectroscopic Study on Ion Solvation and Ion Association of Lithium Tetrafluoroborate in 4‐Ethoxymethyl‐ethylene Carbonate

应用红外及拉曼光谱研究了不同浓度的四氟硼酸锂在4-乙氧甲基-碳酸乙烯酯溶剂中的离子溶剂化和离子缔合现象。环形变谱带和羰基伸缩振动谱带的分裂,以及骨架环振动谱带的迁移和分裂表明,锂离子与溶剂分子间存在着较强的相互作用,这种相互作用是通过溶剂羰基氧原子实现的。利用光谱拟合技术定量计算了表观溶剂化数。随着电解质锂盐浓度的增加,溶剂化数逐渐由4.32降至1.26。此外,四氟硼酸根v1谱带的分裂表明在高浓度溶液中存在着光谱自由的四氟硼酸根、直接接触离子对和离子对二聚体。     

Miscible blends of nitro‐substituted polybenzimidazole and polyetherimide

A novel blend system was prepared by blending organosoluble nitro‐substituted polybenzimidazole (NO₂‐PBI) and polyetherimide (PEI) in a cosolvent at a moderate condition. It was shown that the NO₂‐PBI/PEI blends not only possess tractable processability owing to the enhanced solubility of NO₂‐PBI but also retain the desirable features of unmodified PBI/PEI blends. Apparent miscibility in the blends was observed and attributed to hydrogen‐bonding interactions between N? H groups in NO₂‐PBI and carbonyl groups in PEI. It was revealed that the NO₂‐PBI/PEI blends phase‐separate upon heating above the glass‐transition temperatures. The observed mixing of NO₂‐PBI and PEI in a molecular level, although sustainable only in the glassy region, was shown to lend synergy effects to the physical properties of the blends. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1778–1783, 2001     

Characterization of blends of poly(vinyl chloride) and poly(N‐vinyl pyrrolidone) by FTIR and 13C CP/MAS NMR spectroscopy

Blends of poly(vinyl chloride) (PVC) with Poly(N‐vinyl pyrrolidone) (PVP) were investigated by Fourier infrared spectroscopy (FTIR) and high‐resolution solid‐state ¹³C cross‐polarization/magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR) spectroscopy. The intermolecular interactions between PVP and PVC are weaker than the self‐association of PVP and the inclusion of the miscible PVC results in the decreased self‐association of PVP chains, which was evidenced by the observation of high‐frequency shift of amide stretching vibration bands of PVP with inclusion of PVC. This result was further substantiated by the study of ¹³C CP/MAS spectra, in which the chemical shift of carbonyl resonance of PVP was observed to shift to a high field with inclusion of PVC, indicating that the magnetic shielding of the carbonyl carbon nucleus is increased. The proton spin‐lattice relaxation time in the laboratory frame (T₁ (H)) and the proton spin‐lattice relaxation time in the rotating frame (T_1ρ(H)) were measured as a function of the blend composition to give the information about phase structure. It is concluded that the PVC and PVP chains are intimately mixed on the scale of 20–30Å. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2412–2419, 1999     

Study on the preparation and the self‐assembly of poly(propyleneimine)–poly(styrene) nanoparticles

Using 2‐chloropropionamide derivative of poly(propyleneimine) dendrimer DAB‐dendr‐(NH₂)₃₂ (DAB‐32‐Cl) as the macroinitiator, atom transfer radical polymerization of styrene was successfully carried out in DMF medium. The monodisperse poly(propyleneimine)–polystyrene (dendrimer–PSt) particles with diameters smaller than 100 nm could be prepared. The morphology, size, and size distribution of the dendrimer–PSt particles were characterized by transmission electron microscopy (TEM) and photon correlation spectroscopy (PCS). The effects of reaction temperature, the ratio of St/macroinitiator, and reaction time on the size, and size distribution of the dendrimer–PSt nanoparticles were investigated. In a selective solvent (DMF/H₂O), polymers can self‐assemble into different aggregate configurations such as regular microsphere and wire‐like thread. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2658–2666, 2008     

Dual influence of lithium chloride on the anionic propagation of polystyryllithium in ethereal solvents

The addition of lithium chloride (LiCl) to a solution of polystyryllithium (PStLi) in tetrahydropyran (THP) reduces the rate of propagation of PStLi at a low concentration of the latter but accelerates it at higher concentrations of PStLi. Moreover, the addition of LiCl, which is dimeric in ethereal solutions, increases the conductance of PStLi solutions in tetrahydrofuran (THF) and THP to a much greater extent than expected from the separate conductances of PStLi and LiCl, which is itself even less dissociated than PStLi. These phenomena are fully explained by the dual action of LiCl. Below a certain concentration of PStLi, the dissociation, not of LiCl as such, as claimed before, but of its solvated dimer into free Li⁺ ions and ClLiCl⁻ triple ions provides Li⁺ ions that repress the ionic dissociation of PStLi by a common ion effect. This, in turn, diminishes the concentration of free polystyryl anions, which are the dominating species responsible for the propagation of PStLi, resulting in retardation. However, at higher concentrations of PStLi, Li⁺ ions produced by its dissociation are scavenged by the scavenging action of LiCl dimers, producing quintuple cations. This reduces the concentration of free Li⁺ ions and, therefore, increases the concentration of the reactive free polystyryl anions, resulting in an acceleration of the propagation. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2148–2157, 2002     

Reactive poly(glycidyl methacrylate) microspheres prepared by dispersion polymerization

Poly(glycidyl methacrylate) [poly(GMA)] microspheres of narrow size distribution were prepared in a simple one‐step procedure by dispersion radical polymerization. Depending on the solvent used, poly(GMA) particle size could be controlled in the range of 0.5–4 μm by changing the solubility parameter of the reaction mixture. In N,N′‐dimethylformamide (DMF)/methanol mixture, the particle size increased and the size distribution broadened with decreasing initial solubility parameter. While in the DMF/methanol solvent system, hydroxypropyl cellulose (HPC) or cellulose acetate butyrate (CAB) were taken as steric stabilizers of the dispersion polymerization, poly(vinylpyrrolidone) (PVP) was used in alcoholic media. Contrary to the DMF/methanol system, narrow particle size distributions were obtained with PVP‐stabilized polymerizations in ethanolic, methanolic, propan‐1‐olic or butan‐1‐olic medium. Both the particle size and polydispersity were reduced with increasing stabilizer concentration. If lower molecular‐weight PVP was used, larger microspheres were obtained. Poly(GMA) samples prepared in a neat alcoholic medium virtually quantitatively retained oxirane group content after the polymerization. Reactivity of the poly(GMA) microspheres was confirmed by their hydrolysis and aminolysis. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3855–3863, 2000     

Thermal characterization and solid‐state 13C‐NMR investigation of blends of poly(N‐phenyl‐2‐hydroxytrimethylene amine) and poly(N‐vinyl pyrrolidone)

The miscibility and thermal properties of poly(N‐phenyl‐2‐hydroxytrimethylene amine)/poly(N‐vinyl pyrrolidone) (PHA/PVP) blends were examined by using differential scanning calorimetry (DSC), high‐resolution solid‐state nuclear magnetic resonance (NMR) techniques, and thermogravimetric analysis (TGA). It was found that PHA is miscible with PVP, as shown by the existence of a single composition‐dependent glass transition temperature (T_g) in the whole composition range. The DSC results, together with the ¹³C crosspolarization (CP)/magic angle spinning (MAS)/high‐power dipolar decoupling (DD) spectra of the blends, revealed that there exist rather strong intermolecular interactions between PHA and PVP. The increase in hydrogen bonding and in T_g of the blends was found to broaden the line width of CH—OH carbon resonance of PHA. The measurement of the relaxation time showed that the PHA/PVP blends are homogeneous at least on the scale of 1–2 nm. The proton spin‐lattice relaxation in both the laboratory frame and the rotating frame were studied as a function of the blend composition, and it was found that blending did not appreciably affect the spectral densities of motion (sub‐T_g relaxation) in the mid‐MHz and mid‐KHz frequency ranges. Thermogravimetric analysis showed that PHA has rather good thermal stability, and the thermal stability of the blend can be further improved with increasing PVP content. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 237–245, 1999     

Polymerized ionic liquids: Effects of counter‐anions on ion conduction and polymerization kinetics

A novel imidazolium‐containing monomer, 1‐[ω‐methacryloyloxydecyl]‐3‐(n‐butyl)‐imidazolium (1BDIMA), was synthesized and polymerized using free radical and controlled free radical polymerization followed by post‐polymerization ion exchange with bromide (Br), tetrafluoroborate (BF₄), hexafluorophosphate (PF₆), or bis(trifluoromethylsulfonyl)imide (Tf₂N). The thermal properties and ionic conductivity of the polymers showed a strong dependence on the counter‐ions and had glass transition temperatures (T_g) and ion conductivities at room temperature ranging from 10 °C to −42 °C and 2.09 × 10⁻⁷ S cm⁻¹ to 2.45 × 10⁻⁵ S cm⁻¹. In particular, PILs with Tf₂N counter‐ions showed excellent ion conductivity of 2.45 × 10⁻⁵ S cm⁻¹ at room temperature without additional ionic liquids (ILs) being added to the system, making them suitable for further study as electro‐responsive materials. In addition to the counter‐ions, solvent was found to have a significant effect on the reversible addition‐fragmentation chain‐transfer polymerization (RAFT) for 1BDIMA with different counter‐ions. For example, 1BDIMATf₂N would not polymerize in acetonitrile (MeCN) at 65 °C and only achieved low monomer conversion (< 5%) at 75 °C. However, 1BDIMA‐Tf₂N proceeded to high conversion in dimethylformamide (DMF) at 65 °C and 1BDIMABr polymerized significantly faster in DMF compared to MeCN. NMR diffusometry was used to investigate the kinetic differences by probing the diffusion coefficients for each monomer and counter‐ion in MeCN and DMF. These results indicate that the reaction rates are not diffusion limited, and point to a need for deeper understanding of the role electrostatics plays in the kinetics of free radical polymerizations. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1346–1357     

Synthesis and characterization of amphiphilic poly(N‐vinyl pyrrolidone)‐b‐poly(ε‐caprolactone) copolymers by a combination of cobalt‐mediated radical polymerization and ring‐opening polymerization

An amphiphilic block copolymer of poly(N‐vinyl pyrrolidone)‐b‐poly(ε‐caprolactone) (PVP‐b‐PCL) was synthesized by a combination of cobalt‐mediated radical polymerization (CMRP) and ring‐opening polymerization (ROP). The micellar characteristics of this copolymer were subsequently investigated. PVP (M_n = 11,400, M_w/M_n = 1.32) was synthesized at 20 °C via CMRP using a molar ratio of [VP]₀/[V‐70]₀/[Co]₀ = 150/8/1. The PVP was then reacted with 2,2′‐azobis[2‐methyl‐N‐(2‐hydroxyethyl)propionamide] (VA‐086) to modify its cobalt complex chain end to a hydroxyl group. The cobalt (Co) content in the resulting PVP‐OH was 1.2 ppm, indicating that all of the covalent Co? C bonds were cleaved and reacted with VA‐086, and that the separated cobalt complexes were successfully removed. The ROP of CL was subsequently carried out using the produced PVP‐OH as a macroinitiator at 110 °C. The GPC trace of PVP‐b‐PCL was monomodal without any tailing caused by the residual PVP‐OH, indicating that the initiation efficiency was very high. The critical micelle concentration (CMC) of PVP‐b‐PCL (M_n = 18,000, M_w/M_n = 1.35) was 0.015 mg/mL. The PVP‐b‐PCL micelles were spherical in shape with an average diameter of 105 nm. The nanosized PVP‐b‐PCL micelles show promise as novel drug carriers in biomedical and pharmaceutical applications. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3078–3085, 2009