Synthesis and structural characterization of novel,fluorinated poly(phthalazinone ether)s containing perfluorophenylene moieties

The synthesis and structural characterization of a series of novel, fluorinated poly(phthalazinone ether)s containing perfluorophenylene moieties are described. The monomers, 4‐(4′‐hydroxyaryl)phthalazin‐1(2H)‐ones ( 2a – 2d ), were conveniently and efficiently synthesized from phenols and phthalic anhydride in two steps via 2‐(4′‐hydroxybenzoyl)benzoic acids, which were first obtained by the Friedel–Crafts reaction in good yields and with high stereoselectivity and were then converted into 2a – 2d by fusion with hydrazine. All the polymers were prepared by nucleophilic aromatic substitution (S_NAr) polycondensation between the compounds perfluorobiphenyl and 4‐(4′‐hydroxyaryl)phthalazin‐1(2H)‐ones ( 2a ‐ 2d ). The resulting fluorinated polymers were readily soluble in common organic solvents (e.g., CHCl₃, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, N‐methylpyrrolidone, etc.) at room temperature. Their weight‐average molecular weights and the polydispersities ranged from (7.96–18.25) × 10³ to 1.31–2.71, respectively. Their glass‐transition temperatures varied from 213 to 263 °C. They were all stable up to 390 °C both in air and in argon. The 5% weight‐loss temperatures of these polymers in air and argon ranged from 393–487 to 437–509 °C, respectively. Wide‐angle X‐ray diffraction studies indicated they were all amorphous and could be attributed to the presence of kink nonplanar moiety, phenyl phthalazinone along the polymer backbone. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 925–932, 2004     

Generation of highly stable amidate anion in anionic polymerization of 3‐(triethylsilyl)propyl isocyanate

To study living anionic polymerization, 3‐(triethylsilyl)propyl isocyanate (TEtSPI) monomer was synthesized by hydrosilylation of allylamine with triethylsilane and treatment of the resulting amine with triphosgene. The polymerization of TEtSPI was performed with sodium naphthalenide (Na‐Naph) as an initiator and in the absence and presence of sodium tetraphenylborate (NaBPh₄) as an additive in tetrahydrofuran (THF) at ?78 and at ?98 °C. A highly stabilized amidate anion for living polymerization of isocyanates was generated for the first time with the combined effect of the bulky substituent and the shielding action of the additive NaBPh₄, extending the living character at least up to 120 min at ?98 °C. Even the anion could exist at ?78 °C for 10 min. A block copolymer, poly(n‐hexyl isocyanate)‐b‐poly[(3‐triethylsilyl)propyl isocyanate]‐b‐poly(n‐hexyl isocyanate), was synthesized with quantitative yields and controlled molecular weights via living anionic polymerization in THF at ?78 °C for TEtSPI and ?98 °C for n‐hexyl isocyanate, respectively, with Na‐Naph with three times of NaBPh₄ as a common ion salt. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 933–940, 2004     

Mutual influence of the morphology and capillary rheological properties in nylon/glass‐fiber/liquid‐crystalline‐polymer blends

Nylon‐6/glass‐fiber (GF)/liquid‐crystalline‐polymer (LCP) ternary blends with different viscosity ratios were prepared with three kinds of nylon‐6 with different viscosities as matrices. The rheological behaviors of these blends were characterized with capillary rheometry. The morphology was observed with scanning electron microscopy and polarizing optical microscopy. This study showed that although LCP did not fibrillate in binary nylon‐6/LCP blends, LCP fibrillated to a large aspect ratio in some ternary blends after GF was added. The addition of 5 wt % LCP significantly reduced the melt viscosity of nylon‐6/GF blends to such an extent that some nylon‐6/GF/LCP blends had quite low viscosities, not only lower than those of neat resins and nylon‐6/GF blends but also lower than those of corresponding nylon‐6/LCP blends. The mutual influence of the morphology and rheological properties was examined. The great reduction of the melt viscosity was considered the result of LCP fibrillation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1619–1627, 2004     

Desorption behavior of a surfactant in a linear low‐density polyethylene blend at elevated temperatures

The desorption behavior of a surfactant in a linear low‐density polyethylene (LLDPE) blend at elevated temperatures of 50, 70, and 80 °C was studied with Fourier transform infrared spectroscopy. The composition of the LLDPE blend was 70:30 LLDPE/low‐density polyethylene. Three different specimens (II, III, and IV) were prepared with various compositions of a small molecular penetrant, sorbitan palmitate (SPAN‐40), and a migration controller, poly(ethylene acrylic acid) (EAA), in the LLDPE blend. The calculated diffusion coefficient (D) of SPAN‐40 in specimens II, III, and IV, between 50 and 80 °C, varied from 1.74 × 10^?11 to 6.79 × 10^?11 cm²/s, from 1.10 × 10^?11 to 5.75 × 10^?11 cm²/s, and from 0.58 × 10^?11 to 4.75 × 10^?11 cm²/s, respectively. In addition, the calculated activation energies (E_D) of specimens II, III, and IV, from the plotting of ln D versus 1/T between 50 and 80 °C, were 42.9, 52.7, and 65.6 kJ/mol, respectively. These values were different from those obtained between 25 and 50 °C and were believed to have been influenced by the interference of Tinuvin (a UV stabilizer) at elevated temperatures higher than 50 °C. Although the desorption rate of SPAN‐40 increased with the temperature and decreased with the EAA content, the observed spectral behavior did not depend on the temperature and time. For all specimens stored over 50 °C, the peak at 1739 cm^?1 decreased in a few days and subsequently increased with a peak shift toward 1730 cm^?1. This arose from the carbonyl stretching vibration of Tinuvin, possibly because of oxidation or degradation at elevated temperatures. In addition, the incorporation of EAA into the LLDPE blend suppressed the desorption rate of SPAN‐40 and retarded the appearance of the 1730 cm^?1 peak. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1114–1126, 2004     

Multiphysical modeling and meshless simulation of electric‐sensitive hydrogels

According to a multiphase mixture theory, we have mathematically developed a multiphysical model with chemoelectromechanical coupling considerations, termed the multieffect‐coupling electric‐stimulus (MECe) model, to simulate the responsive behavior of electric‐sensitive hydrogels immersed in a bath solution under an externally applied electric field. For solutions of the MECe model consisting of coupled nonlinear partial differential governing equations, a meshless Hermite–Cloud method with a hierarchical iteration technique has been used for a one‐dimensional steady‐state analysis of a hydrogel strip. The computed results are compared with the experimental data, and there is very good agreement. Simulations within the domains of both hydrogels and surrounding solutions also present distributions of the ionic concentrations and electric potential as well as the hydrogel displacement. The effects of various physical parameters on the response behavior of electric‐stimulus responsive hydrogels are discussed in detail. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1514–1531, 2004     

Effects of poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] on the charge distributions of low‐density polyethylene/polystyrene blends

The effect of the triblock copolymer poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS) on the formation of the space charge of immiscible low‐density polyethylene (LDPE)/polystyrene (PS) blends was investigated. Blends of 70/30 (wt %) LDPE/PS were prepared through melt blending in an internal mixer at a blend temperature of 220 °C. The amount of charge that accumulated in the 70% LDPE/30% PS blends decreased when the SEBS content increased up to 10 wt %. For compatibilized and uncompatibilized blends, no significant change in the degree of crystallinity of LDPE in the blends was observed, and so the effect of crystallization on the space charge distribution could be excluded. Morphological observations showed that the addition of SEBS resulted in a domain size reduction of the dispersed PS phase and better interfacial adhesion between the LDPE and PS phases. The location of SEBS at a domain interface enabled charges to migrate from one phase to the other via the domain interface and, therefore, resulted in a significant decrease in the amount of space charge for the LDPE/PS blends with SEBS. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2813–2820, 2004     

Improved detectability with a polymer-based trapping device in rapid HPLC analysis for ultra-low levels of bisphenol A (BPA) in environmental samples.

A new high-performance liquid chromatography (HPLC) method has been developed to detect ultra-low concentrations of bisphenol-A (BPA) (below 1 ng/L (ppt)) using column switching electrochemical detection (ECD). The results were superior to those obtained from manual pretreatment procedure with membrane stationary phase. BPA is inherently ubiquitous in the environment, including tools and solvents used for its analysis; to obtain meaningful results, therefore, the concentration of the overall BPA contamination must be below the detection limit for BPA using the analytical system. Therefore, purified water for preparing the standard BPA solution must be filtered with a hydrophobic membrane to suppress BPA background levels of contamination. In addition, we investigated methods for effectively preserving environmental water containing BPA. The addition of a small amount of ethylenediaminetetraacetic acid (EDTA) provided good recovery even after overnight storage. By employing these precautionary measures and procedures to reduce BPA contamination from the analytical procedure, we could accurately determine l(-10) ppt of BPA in environmental water samples using a column switching HPLC system.     

Fabrication and Characteristics of Sol-Gel Derived Fluorinated Hybrid Material Films

Fluorinated inorganic-organic hybrid materials (HYBRIMER) were successfully prepared from fluoroalkylsilanes (FASs) containing fluoro-alkyl functions and methacryloxypropyltrimethoxysilane (MPTMS) through a sol-gel process. The influence of concentration and fluoro-alkyl chain lengths of FASs on the physical characteristics of the fluorinated HYBRIMER films was examined. Larger fluorine contents lowered the refractive index within a range, which was closely dependent on the fluoro-alkyl chain lengths of FASs. Thermo-optic coefficients (TOC) were negative values, and the values grew with increasing fluorine contents and fluoro-alkyl chain lengths. Also, the thermal stability is enhanced by addition of fluorine in the HYBRIMER.     

高功率LDA紧密侧面抽运Nd:YLF两级双程离轴放大系统实验研究

 介绍了一台10mm口径两级双程离轴放大系统，实现了对5mm×5mm口径光束的激光放大，耦合系统采用高功率LDA紧密侧面直接抽运棒状Nd:YLF方式。分析并实验研究了在不同抽运电流、放大脉冲与放大器LDA抽运时刻的不同延时及不同注入能量条件下，放大系统及光束每次放大时放大特性的规律。实验得到：在放大系统5mm×5mm软光阑处注入1.58mJ能量时，放大系统可输出129.2mJ能量，能量提取效率达到19.5%，满足该系统的设计指标。