聚合物分散液晶光栅的衍射特性的研究

报道了一种由聚合物分散液晶膜与具有周期性条状电极结构板结合的新型光栅器件，借助于聚合物分散液晶膜的电光特性，这种栅对入射光的散射或衍射取决于对其施加的电压，即它是电场可调的，实验结果显示出当驱动电压超过器件器件阈值电压时，衍射光的强度和衍射斑的可见级次被电场调制，而且它能入射光的线性偏振态变为椭圆偏振态。     

Structure induced by irradiation of femtosecond laser pulse in dyed polymeric materials

We investigated the structures induced by an irradiation of a near‐infrared (NIR) femtosecond laser pulse in dye‐doped polymeric materials {poly(methyl methacrylate) (PMMA), thermoplastic epoxy resin (Epoxy), and a block copolymer of methyl methacrylate and ethyl acrylate‐butyl acrylate [p(MMA/EA‐BA) block copolymer]}. Dyes used were classified into two types—type 1 with absorption at 400 nm and type 2 with no absorption at 400 nm. The 400‐nm wavelength corresponds to the two‐photon absorption region by the irradiated NIR laser pulse at 800 nm. Type 1 dye‐doped PMMA and p(MMA/EA‐BA) block copolymer showed a peculiar dye additive effect for the structures induced by the line irradiation of a NIR femtosecond laser pulse. On the contrary, dye‐doped Epoxy did not exhibit a dye additive effect. The different results among PMMA, p(MMA/EA‐BA) block copolymer, and Epoxy matrix polymers are supposed to be related to the difference of electron‐acceptor properties. The mechanism of this type 1 dye‐additive‐effect phenomenon for PMMA and p(MMA/EA‐BA) block copolymer is discussed on the basis of two‐photon absorption of type 1 dye at 400 nm by the irradiation of a femtosecond laser pulse with 800 nm wavelength and the dissipation of the absorbed energy to the polymer matrix among various transition processes. Dyes with a low‐fluorescence quantum yield favored the formation of thicker grating structures. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2800–2806, 2002     

Synthesis of poly-yne polymers containing transition metals,disilane, disiloxane and phosphine groups in the main chain

The synthesis and characterization of metal poly-yne polymers containing disilane, disiloxane and phosphine groups in the main chain are described. The platinum and palladium poly-yne polymers were synthesized by polycondensation reactions between a metal chloride and an α, ω-bisethynyl complex in amines in the presence of cuprous iodide as a catalyst. The nickel poly-yne polymers were synthesized by an alkynyl ligand exchange reaction between a nickel acetylide and an α, ω-bisethynyl complex in diethylamine in the presence of cuprous iodide as a catalyst. The reaction of the platinum poly-yne polymer, containing disiloxane groups in the main chain, with copper (I) salts afforded adducts of η-²-bonded σ-acetylide polymer complexes. The reactions of the palladium poly-yne polymer, containing phosphine groups in the main chain, with transition-metal carbonyl complexes afforded polymer complexes which have phosphorus in the main chain-transition-metal bonds. A concentrated solution of the platinum poly-yne polymer containing disiloxane groups in the main chain forms a lyotropic liquid crystal in dichloromethane or 1, 2-dichloroethane.     

Predicting the Mechanical Properties of Binary Blends of Immiscible Polymers

We couple a morphological study of an immiscible binary AB mixture with a micromechanical simulation to determine how the spatial distribution of the A and B domains and the interfacial region (interphase) affects the mechanical behavior of the blend. The morphological studies are conducted through a three-dimensional Cahn-Hilliard (CH) simulation. Through the CH calculations, we obtain the size and structure of the domains for different blend compositions. The output of the CH model serves as the input to the Lattice Spring Model (LSM), which consists of a three-dimensional network of springs. In particular, the location of the different phases is mapped onto the LSM lattice and the appropriate force constants are assigned to the LSM sites. A stress is applied to the LSM lattice and we calculate the elastic response of the material. We find that the local stress and strain fields are highly dependent on the morphology of the system. By integrating the morphological and mechanical models, we can isolate how modifications in the composition of the mixture affect the macroscopic behavior. Thus, we can establish how choices made in the components affect the ultimate performance of the material.     

Structural morphology of poly(styrene)-poly(butyl acrylate) polymer-polymer composites studied by dynamic mechanical measurements

The emulsion polymerization process allows production of polymer particles with different structural morphologies. Films obtained after coalescence keep some memory of this morphology, but large modifications can occur during coalescence. In the present case, one of the polymers, polystyrene (PS), exhibits a glass temperature (Tg) much higher than the filmification temperature (close to room temperature), while the other one, poly(butyl acrylate) (PBA), has a much lowerTg. Furthermore, it is well known that dynamic mechanical measurements can be very helpful in providing information on the morphology of polymer materials, i.e., on geometrical and topological arrangement of homopolymer domains. At first, this method was used for comparison of two types of films: i) the first one obtained from structured-core (PS)-shell (PBA) particles, ii) the second one obtained from a blend of homopolymer particles (PS and PBA). It appears that the expected core-shell particles lost their geometric structure in the second film. Second, comparison of the predicted dynamic modulus and experimental data shows that i) strong interactions exist between PS nodules unless their coalescence has occured, leading to an abnormally high modulus at room temperature, ii) after achieving their coalescence, PS forms a more or less continuous phase. Both phenomena strongly depend on the particle size and their respective volume fractions.     

Micromechanics of ferroelectric polymer-based electrostrictive composites

Electrostriction refers to the strain induced in a dielectric by electric polarization, which is usually very small for practical application. In this paper, we present a micromechanical analysis on the effective electrostriction of a ferroelectric polyvinylidene fluoride trifluoroethylene [P(VDF-TrFE)] polymer-based composite, where the exact connections between the effective electrostrictive coefficients and effective elastic moduli are established, and numerical algorithm for the prediction of the effective electrostrictive coefficients of the composite in terms of its microstructural information is developed. From our calculations, enhanced electrostriction in the composite has been demonstrated, and optimal microstructure for electrostriction enhancement has been identified. Our analysis provides a mechanism for the electrostriction enhancement, where the electrostrictive strain several times higher than that of polymer matrix can be obtained, if the microstructure of the composites can be carefully tailored.     

Cationic poly(methacryl oxyethyl trimethylammonium) and its poly(ethylene glycol)‐grafted analogue as capillary coating materials in electrophoresis

Cationic polyelectrolytes were synthesized and used as semipermanent coating materials for capillaries in electrophoresis. The polyelectrolytes used were a homopolymer of poly(methacryl oxyethyl trimethylammonium chloride) (PMOTAC) and its poly(ethylene glycol) (PEG)‐grafted analogue. Two PMOTAC polyelectrolytes, with molar masses of 85,000 and 300,000 g/mol, and PEG‐grafted PMOTAC with a molar mass of 280,000 g/mol were synthesized and then characterized by size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) spectroscopy. Attachment of the polyelectrolytes to the wall of the fused silica capillary for electrophoresis caused the electroosmotic flow (EOF) to reverse. The polyelectrolyte coatings were tested over the pH range 2–11 at different buffer ionic strengths, and the most stable and strongest anodic EOFs were obtained at acidic pH values with low ionic strength buffers. Between runs the capillary is merely rinsed for 2 or 3 min with the background electrolyte solution. With the PMOTAC coatings at pH values ≤5, the RSDs of the EOFs were less than 2.9% after 60 injections. The effects of the molar mass of the polycation and of PEGylation of PMOTAC on the interactions between the polycations and basic proteins were studied at acidic pH values. The differences in the effective electrophoretic mobilities, resolution values, and plate numbers of the proteins with the different coatings were due to the EOF, as demonstrated through calculations of reduced mobilities, relative resolution values, and relative plate numbers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2655–2663, 2007     

SPE电极上Pt单组分及Pt-Au双组分还原态CO_2阳极剥离电化学氧化行为研究

采用循环伏安法，对ＳＰＥＰｔ电极以及ＳＰＥＡｕ－Ｐｔ电极上还原态ＣＯ２的电化学氧化行为研究表明，此类电极的电化学特性与光滑Ｐｔ电极一致：ＣＯ２在氢原子吸附电位区０～２５０ｍＶ（ｖｓ．ＲＨＥ）处，可与电极上化学吸附的氢反应，生成还原态的ＣＯ２，通过线性扫描，还原态ＣＯ２即发生一不可逆电化学氧化过程（阳极剥离）．在ＳＰＥＰｔ系列及ＳＰＥＡｕ－Ｐｔ系列上ＣＯ２的电化学行为表明，当ＳＰＥＰｔ系列上Ｐｔ的载量为２．５ｍＬ的０．０１ｍｏｌ·Ｌ－１Ｈ２ＰｔＣｌ６的Ｐｔ时，对还原态ＣＯ２的电催化活性最好，当Ｐｔ的载量相同时，在ＳＰＥＡｕ－Ｐｔ上，催化剂对还原态ＣＯ２的电化学氧化行为比ＳＰＥＰｔ电极更强，这是由于预先沉积的Ａｕ对后沉积的Ｐｔ有调制作用．     

Pd (II)‐catalyzed vinyl addition polymerization of novel functionalized norbornene bearing dimethyl carboxylate groups

Three novel functionalized polynorbornenes (PNB) with pendant dimethyl carboxylate group (carboxylates—acetate, propionate, and butyrate) are synthesized as a vinyl‐type with a palladium (II) catalyst in high yield. The effects of size of substitutents, molar ratio of monomer to catalyst, solvent polarity, reaction time, and temperature on the polymerization of exo‐norbornene dimethyl propionate were systematically investigated. The low molar ratio and temperature, as well as high polarity of solvent, and long reaction time, are favorable for the enhancement of the monomer conversion, especially, the solvent have an obvious effect on the catalyst activity. The resulting poly(cis‐norbornene‐exo‐2,3‐dimethyl carboxylates) (PNB‐dimethyl carboxylates) show good solubility in common organic solvent and high thermal stability up to 360 °C. The glass transition temperature was detected by DMA at 331, 324, and 318 °C for acetate, propionate, and butyrate, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3391–3399, 2007     

Stereocontrol of diene polymers by topochemical polymerization of substituted benzyl muconates and their crystallization properties

We report the stereocontrol of diene polymers by the topochemical polymerization of alkoxy-substituted benzyl muconates in the solid state. A monomer stacking structure is controlled by the weak intermolecular interactions in the monomer crystals, depending on the structure and position of the alkoxy-substituent. The translational and alternating types of molecular stacking structures in a column provide diisotactic and disyndiotactic polymers, respectively, by the solid-state polymerization under UV and γ-ray irradiation. On the other hand, the meso and racemo structures of the resulting polymers are determined by the molecular symmetry of the used muconate monomers. The various substituted benzyl ester polymers are transformed into the same ethyl ester polymers with the four types of tacticities. The structure and crystallization behavior of the substituted benzyl ester polymers as well as the ethyl ester polymers have been revealed in detail. We clarify the effects of the tacticity on the crystallization property of the stereoregular polymuconates. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4952–4965, 2006