Nonstoichiometric polycondensation I. synthesis of polythioether from dibromomethane and 4,4′-thiobisbenzenethiol

High molecular weight poly(phenylene thioether) ( 3 ) was successfully obtained by the polycondensation of 4,4′-thiobisbenzenethiol ( 1 ) and dibromomethane ( 2 ) with a variety of feed ratios in the presence of 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) in 1-methyl-2-pyrrolidinone (NMP) at 75°C. The resulting polymer showed the maximum inherent viscosity (η_inh) of 0.50 dL/g in 4 h when 1.5 equivalents excess of 2 was used. The model reaction using benzenethiol ( 4 ) and dichloromethane ( 5 ) in the presence of DBU in deuterated dimethylsulfoxide (DMSO-d₆) at 25°C indicated that the rate of the second nucleophilic displacement reaction (k₂) is 61 times faster than that of the first one (k₁). The maximum of theoretical molecular weights calculated at various stoichiometric imbalance (S) under the condition of k₂/k₁ = 61 showed a good agreement with the experimental molecular weights at specific polymerization times.     

General and efficient method for the synthesis of alkoxymethylsilanes

Although alkoxymethylsilanes serve as useful building blocks, various efforts to synthesize them by substitution reaction with an alkoxide ion at the carbon adjacent to the silicon failed. To solve this synthetic problem a new route which is very simple to perform was developed. Bromination of (methoxymethyl)trimethylsilane by using N‐bromosuccinimide/2,2′‐azobisisobutyronitrile (NBS/AIBN) was followed by a substitution by alcohols in the presence of triethylamine to give the corresponding [alkoxy‐­(methoxy)methyl]trimethylsilanes. These acetals can be used directly for the next reduction with di‐isobutylaluminium hydride (DIBAL‐H) or Et₃SiH/BF₃·OEt₂ to give alkoxymethylsilanes in good to moderate yields. The success of the substitution reaction with the alcohols suggests that the mechanism is of somewhat S_N1 by nature and formation of the cationic intermediate seems to release the steric hindrance around the carbon, allowing the attack of alcohols. Copyright © 1999 John Wiley & Sons, Ltd.     

Synthesis of aliphatic polyimides containing adamantyl units

Aliphatic polyimides containing adamantyl units (APIs) were prepared by the poly(addition/condensation) of a dianhydride bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic 2,3 : 5,6-dianhydride with a rigid diamine, 1,3-diaminoadamantane or 3,3′-diamino-1,1′-biadamantyl, and a flexible diamine, 4,4′-methylenebis(cyclohexylamine) or 1,4-cyclohexanediamine. One-step polymerizations were conducted at 80–200°C in m-cresol, producing APIs with inherent viscosities up to 0.53 dL g⁻¹. These APIs are soluble in haloalkanes, m-cresol, and sulfuric acid and show high thermal stability and excellent transparency. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 3584–3590, 1999     

Synthesis and properties of a second‐order nonlinear optical side‐chain polyimide

A thermal stable aromatic polyimide (PI) with side‐chain second‐order nonlinear optical (NLO) chromophores has been developed. The PI was prepared by the ring‐opening polyaddition of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride with a new diamine having two N‐ethyl‐N‐[4‐[(6‐chlorobenzothiazol‐2‐yl)diazenyl]phenyl]‐2‐aminoethanol units as the NLO chromophore, followed by poling during or after the thermal imidization process. The resulting PI had number and weight‐average molecular weights (M_n, M_w) of 25,000 and 80,000, respectively, and a relatively high glass transition temperature of 180°C. The second harmonic coefficient (d₃₃) of PI at the wavelength of 1.064 μm was 138 pm/V (329.6 × 10⁻⁹ esu) and remained unchanged at elevated temperatures. The corona poling process of the NLO‐substituted poly(amic acid) to the PI was also studied in detail by measuring the second harmonic generation (SHG) from the polymer films. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1321–1329, 1999     

Graft copolymers having hydrophobic backbone and hydrophilic branches. XXIII. Particle size control of poly(ethylene glycol)-coated polystyrene nanoparticles prepared by macromonomer method

Monodisperse polymeric nanospheres, which consist of polystyrene cores and poly(ethylene glycol) (PEG) branches on their surfaces, were prepared by the dispersion copolymerization of styrene (St) with PEG macromonomers that had a methacryloyl (MMA-PEG) or p-vinylbenzyl (St-PEG) end group in various organic solvent/water media. Electron spectroscopy for chemical analysis (ESCA) of the nanosphere surfaces indicated that PEG macromonomer chains were favorably located on their surfaces. The morphologies of the nanospheres were observed via a scanning electron micrograph (SEM), and particle sizes were estimated by a submicron particle analyzer. When both the concentration of macromonomers and molecular weight were higher, small nanospheres in diameter were obtained. Larger nanospheres in diameter were obtained using macromonomers with low molecular weight at lower concentration. The functions that correlate the diameter (D_n) on different concentration units were D_n = K[St]^0.64[MMA-PEG]^{−0.53±0.01}[I]^−0.49 and D_n = K[St]^0.80[St-PEG]^{−0.69±0.01}[I]^−0.22, where [I], [St], [MMA-PEG], and [St-PEG] are initiator, styrene, MMA-PEG, and St-PEG macromonomer concentration in feed, respectively. When the reaction parameters such as the molecular weight of the macromonomers were properly chosen, the particle size could be controlled in a range from ca. 80 to 3100 nm. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2155–2166, 1999     

Dissociation behavior of poly(α‐hydroxy acrylic acid)

Dissociation behavior of poly(α‐hydroxy acrylic acid) (PHA) was investigated by potentiometric titration in the presence of NaCl and/or divalent metal chlorides. It was found that pH values of PHA aqueous solutions increased with time when the degree of dissociation, α, is high (α ≧ 0.5 for NaCl system) and decreased in the lower α region (α < 0.5 for NaCl). The increase of pH was attributed to lactone ring formation that occurs between a carboxyl group and a neighbor hydroxyl group upon protonation to the former, and the decrease of pH to an induction effect by lactone ring to −COOH group. The pH‐increasing process was analyzed by assuming it being of a first order to obtain a time constant. On the basis of time constant thus estimated and pKa values for divalent counterion systems, a correlation between counterion binding and lactone ring formation was discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1523–1531, 1999     

Ion–ion interactions of LiPF6 and LiBF4 in propylene carbonate solutions

Self-diffusion coefficients of Li⁺ D_Li⁺, PF₆⁻ D_PF6⁻ and solvent propylene carbonate (PC) D_PC in LiPF₆−PC solutions were determined at 298 K by the pulse gradient spin echo (PGSE) NMR technique over the salt concentration range of 0.1–3.0 M (M = mol dm^– 3). The order of the diffusion coefficients was found to be D_Li⁺ < D_PF6⁻ < D_PC over the concentration range examined, and they were monotonically decreased with increasing the salt concentration. Haven ratio Λ/Λ_NMR, where Λ and Λ_NMR represent the ionic conductivity measured electrochemically and that estimated via the Nernst-Einstein equation using the diffusion coefficient, respectively, was evaluated as the measure of the ion–ion interaction in the LiPF₆–PC solutions. Though Λ/Λ_NMR values for LiPF₆-solutions decrease with increasing the salt concentration, they were greater than those for LiBF₄–PC solutions over the whole concentration range examined, which indicates that the ion pair formation ability of PF₆^– ion is weaker than that of the BF₄^– ion. The smaller value of the ionic conductivity for the highly concentrated LiPF₆–PC solution (above 2.0 M) than that of the LiBF₄-solutions can be attributed to the more rapidly increased viscosity relative to the LiBF₄-solution. Classic molecular dynamics (MD) simulations for the respective LiPF₆ and LiBF₄-solution of 0.5 and 1.0 M were also carried out based on the effective pair potentials. Diffusion coefficients, ionic conductivity and Haven ratio for these solutions were calculated from MD trajectories, and they qualitatively agree with those evaluated by experiments. Pair correlation functions g_LiO(r) (for Li⁺–O (PC) pair) and g_LiPF6(r) (for Li⁺–PF₆^– pair) or g_LiBF4(r) (for Li⁺–BF₄^– pair) revealed that the lithium ion weakly forms the contact ion pairs with PF₆^–, whilst strongly with BF₄^–, which supports the present experimental results. Moreover, the simulation results show that both anions in the contact ion pairs predominantly take the monodentate form, which is in contrast to the multidentate coordination predicted by ab initio calculation in gas phase.     

Micromachining and surface processing of the super-hard nano-polycrystalline diamond by three types of pulsed lasers

Laser beam micromachining was applied to super-hard nano-polycrystalline diamond (NPD) synthesized by the direct conversion of graphite at high pressure and high temperature. Three types of pulsed lasers were tested: nanosecond near-infrared, nanosecond near-ultraviolet, and femtosecond near-infrared lasers. The latter two were also applied for synthetic single crystal of diamond to compare the results with those of the NPD. It was demonstrated that the nanosecond near-infrared laser was the most efficient device for rough shaping of the NPD, while the ultraviolet and femtosecond lasers give satisfactory results for precise surface finishing of it. The properties of the laser-processed surfaces were analyzed by scanning and transmission electron microscopy, laser scanning microscopy, and micro Raman spectroscopy. These analyses demonstrated that the three types of lasers play different and complementary roles, and that their combination is the best suitable solution for micromachining of the hardest diamond into any desired shapes.