New ligands for the Fe(III)‐mediated reverse atom transfer radical polymerization of methyl methacrylate

A series of (di)picolinic acids and their derivates are investigated as novel complexing tridentate or bidentate ligands in the iron‐mediated reverse atom transfer radical polymerization of methyl methacrylate in N,N‐dimethylformamide at 100 °C with 2,2′‐azobisisobutyrontrile as an initiator. The polymerization rates and polydispersity indices (1.32–1.8) of the resulting polymers are dependent on the structures of the ligands employed. Different iron complexes may be involved in iron‐mediated reverse atom transfer radical polymerization, depending on the type of acid used. ¹H NMR spectroscopy has been used to study the structure of the resulting polymers. Chain‐extension reactions have been performed to further confirm the living nature of this catalytic system. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2912–2921, 2006     

Nanostructured thermoset epoxy resin templated by an amphiphilic poly(ethylene oxide)‐block‐poly(dimethylsiloxane) diblock copolymer

An amphiphilic poly(ethylene oxide)‐block‐poly(dimethylsiloxane) (PEO–PDMS) diblock copolymer was used to template a bisphenol A type epoxy resin (ER); nanostructured thermoset blends of ER and PEO–PDMS were prepared with 4,4′‐methylenedianiline (MDA) as the curing agent. The phase behavior, crystallization, hydrogen‐bonding interactions, and nanoscale structures were investigated with differential scanning calorimetry, Fourier transform infrared spectroscopy, transmission electron microscopy, and small‐angle X‐ray scattering. The uncured ER was miscible with the poly(ethylene oxide) block of PEO–PDMS, and the uncured blends were not macroscopically phase‐separated. Macroscopic phase separation took place in the MDA‐cured ER/PEO–PDMS blends containing 60–80 wt % PEO–PDMS diblock copolymer. However, the composition‐dependent nanostructures were formed in the cured blends with 10–50 wt % PEO–PDMS, which did not show macroscopic phase separation. The poly(dimethylsiloxane) microdomains with sizes of 10–20 nm were dispersed in a continuous ER‐rich phase; the average distance between the neighboring microdomains was in the range of 20–50 nm. The miscibility between the cured ER and the poly(ethylene oxide) block of PEO–PDMS was ascribed to the favorable hydrogen‐bonding interaction. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3042–3052, 2006     

The existence of Chern-Simons vortices

A new type of vortices called Chern-Simons vortices is considered and the existence is established.     

Acyl chloride‐facilitated condensation polymerization for the synthesis of heat‐sensitive poly(anhydride‐ester)s

We succeeded in developing the acyl chloride‐facilitated condensation polymerization method for the synthesis of new poly(anhydride‐ester)s with aromatic side groups, which cannot be polymerized by the classic melt condensation polymerization method. Using chlorinated and acylated carboxylic acids as the intermediates, the polymerization was carried out at low temperatures of 120 or 135 °C to yield pure poly(anhydride‐ester)s of molecular weights as high as 1.55 × 10⁵ with minimal side‐reactions. A homogeneous route of preparation was developed and optimized, using butyric anhydride as the acylating reagent and oxalyl chloride as the chlorinating reagent. A comparison of the mechanisms of the classic method and the new method indicates that the effects of transacylation—cyclization and oligomer formation—were greatly reduced due to the high reactivity of carboxylic acid chloride and the steric effect of bulky acyl groups. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5899–5915, 2007     

A method to collect an infrared spectrum in solution.

Herein we report a new method to collect a qualified infrared spectrum of a solute in solution by two solvent cells with different thickness during background single-beam spectrum scanning. By collecting the background spectrum with two cells (two stages), we successfully achieved accurate solvent compensation between a sample and a reference, namely, the solvent amounts in the sample and background measurements could become congruent. Therefore, the solvent bands were thoroughly suppressed in the infrared spectrum and a qualified spectrum of the solute was obtained.     

Mono-dispersed cross-linked polystyrene micro-spheres prepared by seed swelling polymerization method

A two-step swelling procedure was adopted to synthesize mono-dispersed and highly cross-linked poly (St-divinylbenzene) particles with PSt micro-spheres (1.80 μm in diameter). The PSt micro-spheres were prepared by a dispersion polymerization method and used as seeds. The effects of monomer concentration, ratio of ethanol to water, swelling reagents, crosslinking reagents, swelling temperature and agitation speed on particle size were investigated in detail. The morphologies and size distributions of these micro-spheres were examined by SEM and particle size analysis (PSA). The T _g of the micro-spheres was measured by DSC. The results indicate that the particles (6.20 μm in diameter) exhibit excellent mono dispersed property and high crosslinking degree when the concentration of the swelling reagent was 25%, the concentration of the crosslinking reagents was 23%, the swelling temperature was 30°C and the stirring speed was 150 r/min. __________ Translated from Chinese Journal of Applied Chemistry, 2007, 24(11): 1289–1294     

Structural hierarchy of rock masses and the mechanisms of its formation

The formation mechanisms for the structural hierarchy in geological media are discussed. It is shown that the formation of such a hierarchy is caused by certain external and internal circumstances. The first ones consist in the fact that, because of external actions, the Earth’s poles continuously execute the translational and rotational motions responsible for a regular structure of rock fracture and for the appearance of the scale factor √2. The second ones consist in the fact that, under the action of many random factors and because of external actions, during the formation of geological media there appear dissipative structures and, hence, some self-similar fractal structures are formed.     

Miscibility and phase structure of binary blends of polylactide and poly(methyl methacrylate)

Blends of amorphous poly(DL‐lactide) (DL‐PLA) and crystalline poly(L‐lactide) (PLLA) with poly(methyl methacrylate) (PMMA) were prepared by both solution/precipitation and solution‐casting film methods. The miscibility, crystallization behavior, and component interaction of these blends were examined by differential scanning calorimetry. Only one glass‐transition temperature (T_g) was found in the DL‐PLA/PMMA solution/precipitation blends, indicating miscibility in this system. Two isolated T_g's appeared in the DL‐PLA/PMMA solution‐casting film blends, suggesting two segregated phases in the blend system, but evidence showed that two components were partially miscible. In the PLLA/PMMA blend, the crystallization of PLLA was greatly restricted by amorphous PMMA. Once the thermal history of the blend was destroyed, PLLA and PMMA were miscible. The T_g composition relationship for both DL‐PLA/PMMA and PLLA/PMMA miscible systems obeyed the Gordon–Taylor equation. Experiment results indicated that there is no more favorable trend of DL‐PLA to form miscible blends with PMMA than PLLA when PLLA is in the amorphous state. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 23–30, 2003     

Living polymerization of styrene initiated by mercaptan/ε‐caprolactam

The bulk polymerization of styrene initiated by ?‐caprolactam (CL) and n‐dodecyl mercaptan (RSH) has been explored. This novel polymerization system shows living characteristics. For example, the molecular weight of the resulting polymers increases with conversion, and the system has the ability to form diblock copolymers and so forth. The polymer chain end contains thiol and lactam structures, which we have investigated with Fourier transform infrared, ¹H NMR, and ¹³C NMR techniques. Electron spin resonance spectra and theoretical calculations by the Hartree–Fock methods have been used to examine the mechanism. The results reveal that the initial polymerization starts from thiol via a chain‐transfer reaction, and the propagation proceeds by the insertion of a monomer between the terminal group and the intermediate structure of lactam. Finally, the polymerization kinetics have been examined. The polymerization rate varies linearly with the concentration of CL and RSH, and this confirms the mechanism. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4976–4993, 2004