Synthesis and characterization of a polyfluorene containing carbazole and oxadiazole dipolar pendent groups and its application to electroluminescent devices

We have synthesized a blue‐light‐emitting polyfluorene (PF) derivative ( PF‐CBZ‐OXD ) that presents bulky hole‐transporting carbazole and electron‐transporting oxadiazole pendent groups functionalized at the C‐9 positions of alternating fluorene units. The results from photoluminescence and electrochemical measurements indicate that both the side chains and the PF main chain retain their own electronic characteristics in the copolymer. An electroluminescent device incorporating this polymer as the emitting layer was turned on at 4.5 V; it exhibited a stable blue emission with a maximum external quantum efficiency of 1.1%. Moreover, we doped PF‐CBZ‐OXD and its analogue PF‐TPA‐OXD with a red‐light‐emitting iridium phosphor for use as components of phosphorescent red‐light emitters to investigate the effect of the host's HOMO energy level on the degree of charge trapping and on the electrophosphorescent efficiency. We found that spectral overlap and individual energy level matching between the host and guest were both crucial features affecting the performance of the electroluminescence devices. Atomic force microscopy measurements indicated that the dipolar nature of PF‐CBZ‐OXD , in contrast to the general nonpolarity of polydialkylfluorenes, provided a stabilizing environment that allowed homogeneous dispersion of the polar iridium triplet dopant. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2925–2937, 2007     

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.     

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     

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.     

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