Controlled/living polymerization of 2‐(diethylamino)ethyl methacrylate and its block copolymer with tert‐butyl methacrylate by atom transfer radical polymerization

Polymerization of 2‐(diethylamino)ethyl methacrylate (DEAEMA) via homogeneous atom transfer radical polymerization under various reaction conditions is described. The effects of the initiators and solvents were examined. With 1,1,4,7,10,10‐hexamethyl triethylenetetramine/copper(I) chloride/p‐toluenesulfonyl chloride as the ligand/catalyst/initiator system in methanol, poly(DEAEMA) with a polydispersity index as low as 1.07 was synthesized. Kinetic studies demonstrated the polymerization was very well controlled and exhibited the living characteristic of the process. Well‐defined block copolymers of DEAEMA and tert‐butyl methacrylate (tBMA) were successfully synthesized. The copolymers could be synthesized with equally good results by starting with either p(DEAEMA) or p(tBMA) as the macroinitiators. However, only the macroinitiators terminated with chlorine should be used. The corresponding macroinitiators with bromine as a transferable group did not yield well‐defined copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2688–2695, 2003     

Annealing behavior of gel‐spun polyethylene fibers at temperatures lower than needed for significant shrinkage

The annealing at 373 K of ultrastrong, gel‐spun polyethylene (PE) has been studied. At this temperature, the fibers show no significant shrinkage. Still, a significant decrease in the mechanical properties is observed. The fibers have been analyzed with differential scanning calorimetry (DSC), temperature‐modulated differential scanning calorimetry (TMDSC), atomic force microscopy (AFM), and small‐angle X‐ray scattering (SAXS). During the annealing, the glass transition of the intermediate phase is exceeded, as shown by DSC. When split for structure analysis by AFM, the annealed fibers undergo plastic deformation around the base fibrils instead of brittle fracture. The quasi‐isothermal TMDSC experiments are compared to the minor structural changes seen with SAXS and AFM. The loss of performance of the PE fibers at 373 K is suggested to be caused by the oriented intermediate phase, and not by major changes in the structure or morphology. The overall metastable, semicrystalline structure is shown by TMDSC to posses local regions that can melt reversibly. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 403–417, 2003     

Dynamic mechanical thermal analysis transitions of partially and fully substituted cellulose fatty esters

The main transitions of cellulose fatty esters with different degrees of substitution (DSs) were investigated with dynamic mechanical thermal analysis. Two distinct main relaxations were observed in partially substituted cellulose esters (PSCEs). They were attributed to the glass‐transition temperature and to the chain local motion of the aliphatic substituents. The temperatures of both transitions decreased when DS or the number of carbon atoms (n) of the acyl substituent increased. Conversely, all the transitions of fully substituted cellulose esters occurred within a narrow temperature range, and they did not vary significantly with n. This phenomenon was explained by the formation of a crystalline phase of the fatty substituents. The presence of few residual OH groups in PSCEs was responsible for a large increase in the storage bending modulus, and it eliminated the effect of n on damping. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 281–288, 2003     

2‐connected 7‐coverings of 3‐connected graphs on surfaces

An m‐covering of a graph G is a spanning subgraph of G with maximum degree at most m. In this paper, we shall show that every 3‐connected graph on a surface with Euler genus k ≥ 2 with sufficiently large representativity has a 2‐connected 7‐covering with at most 6k ? 12 vertices of degree 7. We also construct, for every surface F² with Euler genus k ≥ 2, a 3‐connected graph G on F² with arbitrarily large representativity each of whose 2‐connected 7‐coverings contains at least 6k ? 12 vertices of degree 7. © 2003 Wiley Periodicals, Inc. J Graph Theory 43: 26–36, 2003     

Simple and efficient cleavage reaction of the boc group in heterocyclic compounds

Dedicated to the memory of Pr. Ladjama Daif A series of chiral cyclosulfamides have been synthesized by alkaline cyclisation starting from N‐benzoylamino acids (Ala, Val, Leu, Phe) derivatives and chlorosulfonyl isocyanate. A simplified and regioselective deprotection of the cyclic compounds (cyclosulfamides) containing the tert‐butyloxycarbonyl group (Boc) has been achieved in good yield by fusion under reduced pressure.     

An expedient synthesis of an isofervenulin analogue

An efficient approach has been developed for the synthesis of an isofervenulin analogue 1 employing a one‐pot condensation‐substitution reaction of a chlorocarboethoxytriazine (electrophile) with a urea (nucleophile). The resulting cyclization reaction resulted in the synthesis of a pyrimido‐heterocycle in good yield in either acidic or basic media. The former was assisted by utilizing trimethylsilyl chloride.     

Kristallstruktur des Zinkamids Zn[N(SiMe3)2]2

Crystal Structure of the Zinc Amide Zn[N(SiMe₃)₂]₂ X‐ray quality crystals of Zn[N(SiMe₃)₂]₂ (monoclinic, P2₁/c) are obtained by sublimation of the zinc amide Zn[N(SiMe₃)₂]₂ at —30 °C in vacuo (300 torr). According to the result of the X‐ray structural analysis, Zn[N(SiMe₃)₂]₂ contains an almost linear N‐Zn‐N unit with two short N‐Zn bonds.     

Transition‐metal‐catalyzed reactions of 5‐methylene‐2‐oxazolidinone and 5‐methylene‐1,3‐thiazolidine‐2‐thione with isocyanates

5‐Methylene‐2‐oxazolidinone (1) and 5‐methylene‐1,3‐thiazolidine‐2‐thione (4) react with various isocyanates to give the corresponding urethanes 3 and 5 in high yields in the presence of palladium(0) or palladium(II) catalyst under mild reaction conditions. A mechanism is proposed. Copyright © 2003 John Wiley & Sons, Ltd.     

Relaxor behavior of (Ba,Sr)(Zr,Ti)O3 ferroelectric ceramics

We examine the ferroelectric-relaxor behavior of (Ba_0.65Sr_0.35)(Zr_0.35Ti_0.65)O₃ (BSZT) ceramics in the temperature range from 80 to 380 K. A broad dielectric maximum, which shifts to higher temperature with increasing frequency, signifies the relaxor-type behavior of these ceramics. The value of the relaxation parameter γ∼2 estimated from the linear fit of the modified Curie-Weiss law, indicates the relaxor nature of the BSZT ceramics. The dielectric relaxation rate follows the Vogel-Fulcher relation with T_VF=107 K, E_a=0.121 eV, and ν₀=6.83×10¹⁴ Hz, further supports such relaxor nature. The slim P-E hysteresis loop and ‘butterfly’ shape dc bias field dependence of permittivity at T>T_m (T_m, the temperature of permittivity maximum) clearly signifies the occurrence of nanopolar clusters, which is the typical characteristic of ferroelectric relaxor. At 300 K and 10 kHz, the dielectric constant and loss tan δ are ∼1100 and 0.0015, respectively. The high tunability (∼25%) and figure of merit (∼130) at room temperature show that the BSZT ceramics could be a promising candidate for tunable capacitor applications.