Polymerization behaviors of racemic and chiral amphiphilic monomers in organized bilayer membranes of lamellar liquid crystalline phase

A racemic amphiphilic monomer, n‐dodecyl glyceryl itaconate (DGI), forms bilayer membranes in water in the presence of small amount of ionic cosurfactant and shows iridescent color. A chiral DGI, S‐DGI, also shows an iridescent property, but with a rather red shift in the color, which can be ascribed to the increased packing density of the monomer in the bilayer membranes. Chrial DGI has a more compact packing density than racemic one owing to closer distance between the monomer molecules; the conversion rate, however, is slower than that of racemic one when H₂O₂ is used as an initiator. When the initiator is changed to an amphiphilic one, 4‐(2‐hydroxyethoxy) phenyl‐(2‐hydroxy‐2‐propyl) ketone (Irgacure 2959), the chiral DGI shows even a little faster conversion rate than that of racemic one. The NMR chemical shift results of protons in benzene ring show that the molecules of Irgacure 2959 insert into the bilayer membranes. The molecular weights of the corresponding polymers prove that the initiation by H₂O₂ is restricted compared to that by Irgacure 2959. It is concluded that the decelerated polymerization behavior of chiral DGI initiated by H₂O₂ is a result of limited diffusion of the initiator into the lamellar bilayer structures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4891–4900, 2007     

Rhythmic growth of ring‐banded spherulites in blends of liquid crystalline methoxy‐poly(aryl ether ketone) and poly(aryl ether ether ketone)

Rhythmic growth of ring‐banded spherulites in blends of liquid crystalline methoxy‐poly(aryl ether ketone) (M‐PAEK) and poly(aryl ether ether ketone) (PEEK) has been investigated by means of differential scanning calorimetry (DSC), polarized light microscopy (PLM), and scanning electron microscopy (SEM) techniques. The measurements reveal that the formation of the rhythmically grown ring‐banded spherulites in the M‐PAEK/PEEK blends is strongly dependent on the blend composition. In the M‐PAEK‐rich blends, upon cooling, an unusual ring‐banded spherulite is formed, which is ascribed to structural discontinuity caused by a rhythmic radial growth. For the 50:50 M‐PAEK/PEEK blend, ring‐banded spherulites and individual PEEK spherulites coexist in the system. In the blends with PEEK as the predominant component, M‐PAEK is rejected into the boundary of PEEK spherulites. The cooling rate and crystallization temperature have great effect on the phase behavior, especially the ring‐banded spherulite formation in the blends. In addition, the effects of M‐PAEK phase transition rate and phase separation rate on banded spherulite formation is discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3011–3024, 2007     

Effects of diamines and their fluorinated groups on the color lightness and preparation of organosoluble aromatic polyimides from 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]‐hexafluoropropane

To investigate the position and amount of the CF₃ group affecting the coloration of polyimides (PIs), we prepared 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]hexafluoropropane ( 2 ) with four CF₃ groups with 2‐chloro‐5‐nitrobenzotrifluoride and 2,2‐bis(4‐hydroxyphenol)hexafluoropropane. A series of soluble and light‐colored fluorinated PIs ( 5 ) were synthesized from 2 and various aromatic dianhydrides ( 3a – 3f ). 5a – 5f had inherent viscosities ranging from 0.80 to 1.19 dL/g and were soluble in amide polar solvents and even in less polar solvents. The glass‐transition temperatures of 5 were 221–265 °C, and the 10% weight‐loss temperatures were above 493 °C. Their films had cutoff wavelengths between 343 and 390 nm, b* values (a yellowness index) ranging from 5 to 41, dielectric constants of 2.68–3.01 (1 MHz), and moisture absorptions of 0.03–0.29 wt %. In a comparison of the PI series 6 – 8 based on 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane, 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]propane, and 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane, we found that the CF₃ group close to the imide group was more effective in lowering the color; this means that CF₃ of 5 , 7 , and 8f was more effective than that of 6c . The color intensity of the four PI series was lowered in the following order: 5 > 7 > 6 > 8 . The PI 5f , synthesized from diamine 2 and 4,4′‐hexafluoroisopropylidenediphthalic anhydride, had six CF₃ groups in a repeated segment, so it exhibited the lightest color among the four series. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 922–938, 2003     

Living/controlled radical copolymerization of N‐substituted maleimides with styrene in 1‐butyl‐3‐methylimidazolium hexafluorophosphate and anisole

The atom transfer radical copolymerization of N‐substituted maleimides such as N‐phenylmaleimide (PhMI), N‐cyclohexylmaleimide (ChMI), and N‐butylmaleimide (NBMI) with styrene initiated with dendritic polyarylether 2‐bromoisobutyrates in an ionic liquid, 1‐butyl‐3‐methylimidazolium hexafluorophosphate ([bmim][PF₆]), at room temperature and anisole at 110 °C was investigated. The dendritic‐linear block copolymers obtained in ionic liquid possessed well‐defined molecular weight and low polydispersity (1.05 < M_w/M_n < 1.32) and could be used as a macroinitiator for chain‐extension polymerization, suggesting the living nature of the reaction system. The ionic liquids containing catalyst could be recycled in the atom transfer radical polymerization systems without further treatment. Compared with polymerization conducted in anisole, the polymerization in ionic liquid had a stronger tendency for alternation. The tendency for alternation decreased in the order PhMI > NBMI > ChMI in [bmim][PF₆] and PhMI > ChMI > NBMI in anisole. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2156–2165, 2003     

Reply to Nathan: How to reconstruct the causal argument

Nicholas Nathan tries to resist the current version of the causal argument for sense-data in two ways. First he suggests that, on what he considers to be the correct re-construction of the argument, it equivocates on the sense of proximate cause. Second he defends a form of disjunctivism, by claiming that there might be an extra mechanism involved in producing veridical hallucination, that is not present in perception. I argue that Nathan’s reconstruction of the argument is not the appropriate one, and that, properly interpreted, the argument does not equivocate on proximate cause. Furthermore, I claim that his postulation of a modified mechanism for hallucinations is implausibly ad hoc.     

Assessment of two‐equation turbulence modelling for high Reynolds number hydrofoil flows

This paper presents an evaluation of the capability of turbulence models available in the commercial CFD code FLUENT 6.0 for their application to hydrofoil turbulent boundary layer separation flow at high Reynolds numbers. Four widely applied two‐equation RANS turbulence models were assessed through comparison with experimental data at Reynolds numbers of 8.284×106 and 1.657×107. They were the standard k–εmodel, the realizable k–εmodel, the standard k–ωmodel and the shear‐stress‐transport (SST) k–ωmodel. It has found that the realizable k–εturbulence model used with enhanced wall functions and near‐wall modelling techniques, consistently provides superior performance in predicting the flow characteristics around the hydrofoil. Copyright © 2004 John Wiley & Sons, Ltd.     

Synthesis of a soluble pyrrole copolymer with phenetidine

A new series of copolymers was synthesized through the oxidative polymerization of pyrrole (PY) and o‐phenetidine (PHT) with inorganic oxidants in acidic media. The polymerization parameters including the mixing method of the oxidant with the comonomer, the comonomer ratio, the time, the temperature, the oxidant, the organic medium, and the acid were systematically optimized for the synthesis of copolymers with high yields, intrinsic viscosities, and solubility. The resultant copolymers were characterized by elemental analysis, infrared, ultraviolet–visible, solution high‐resolution ¹H NMR and solid‐state high‐resolution ¹³C NMR, circular dichroism spectroscopy, and cyclic voltammetry. The results showed that the PY observed content in the copolymers was much higher than the PY feed content. The regular variation of the polymerization yield, intrinsic viscosity, solubility, macromolecular structure, and electroactivity of the resulting polymers with the comonomer ratio, together with the complete solubility of a PY/PHT (10/90) polymer in highly polar solvents, indicated the formation of real random copolymers containing both PY and PHT units rather than a mixture of two homopolymers. However, the polymers containing more than 59 mol % PY were not homogeneous copolymers consisting of soluble and insoluble parts. A semiquantitative relationship between the polymerization yield or solubility of the copolymers and the polarity index of the organic solvents was examined. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2073–2092, 2004     

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     

Combined effects of clay modifications and compatibilizers on the formation and physical properties of melt‐mixed polypropylene/clay nanocomposites

The melt mixing technique was used to prepare various polypropylene (PP)‐based (nano)composites. Two commercial organoclays (denoted 20A and 30B) served as the fillers for the PP matrix, and two different maleated (so‐called) compatibilizers (denoted PP‐MA and SMA) were employed as the third component. The results from X‐ray diffraction (XRD) and transmission electron microscope (TEM) experiments revealed that 190 °C was an adequate temperature for preparing the nanocomposites. Nanocomposites were achieved only if specific pairs of organoclay and compatibilizer were simultaneously incorporated in the PP matrix. For example, PP/20A(5 wt %)/PP‐MA(10 wt %) and PP/30B(5 wt %)/SMA(5 wt %) composites exhibited nanoscaled dispersion of 20A or 30B in the PP matrix. Differential scanning calorimetry (DSC) results indicated that the organoclays served as nucleation agents for the PP matrix. Generally, their nucleation effectiveness increased with the addition of compatibilizers. The thermal stability enhancement of PP after adding 20A was confirmed with thermogravimetric analysis (TGA). The enhancement became more evident as a suitable compatibilizer was further added. However, for the 30B‐included composites, thermal stability enhancement was not evident. The dynamic mechanical properties (i.e., storage modulus and loss modulus) of PP increased as the nanocomposites were formed; the properties increment corresponded to the organoclay dispersion status in the matrix. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4139–4150, 2004     

Behavior and surface energies of polybenzoxazines formed by polymerization with argon,oxygen, and hydrogen plasmas

Polybenzoxazine (PBZZ) thin films can be fabricated by the plasma‐polymerization technique with, as the energy source, plasmas of argon, oxygen, or hydrogen atoms and ions. When benzoxazine (BZZ) films are polymerized through the use of high‐energy argon atoms, electronegative oxygen atoms, or excited hydrogen atoms, the PBZZ films that form possess different properties and morphologies in their surfaces. High‐energy argon atoms provide a thermodynamic factor to initiate the ring‐opening polymerization of BZZ and result in the polymer surface having a grid‐like structure. The ring‐opening polymerization of the BZZ film that is initiated by cationic species such as oxygen atoms in plasma, is propagated around nodule structures to form the PBZZ. The excited hydrogen atom plasma initiates both polymerization and decomposition reactions simultaneously in the BZZ film and results in the formation of a porous structure on the PBZZ surface. We evaluated the surface energies of the PBZZ films polymerized by the action of these three plasmas by measuring the contact angles of diiodomethane and water droplets. The surface roughness of the films range from 0.5 to 26 nm, depending on the type of carrier gas and the plasma‐polymerization time. By estimating changes in thickness, we found that the PBZZ film synthesized by the oxygen plasma‐polymerization process undergoes the slowest rate of etching in CF₄ plasma. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4063–4074, 2004