Solid-State polymerization of the binary mixture of methacrylate and liquid-crystalline compound by electron beam

Solid-state polymerization of a binary mixture of nonliquid-crystalline monomer and liquidcrystalline compound was carried out using electron beam. The monomers were benzoic acid containing 4-[ω-(meth)acryloyloxyalkyloxy] benzoic acids, in which the alkylene spacer was ethylene, hexamethylene, or undecamethylene. The conversion yield of monomer to polymer to a large extent increased with increasing content of a liquid-crystalline compound with a terminal carboxylic group, such as 4-n-alkyloxybenzoic acid, while the addition of a liquid-crystalline compound without terminal carboxylic group did not affect polymerization of the monomer. Phase diagrams of the mixture of monomer and liquid-crystalline compound were examined using cross-polarizing microscopy and differential scanning calorimetry (DSC). All mixtures of monomer and 4-n-alkyloxybenzoic acid or liquid-crystalline compound without terminal carboxylic group showed liquid-crystallinity in a broad composition range. It was concluded that liquid-crystalline compounds with terminal carboxylic acid may form hydrogen bondings with methacrylate or acrylate monomer having terminal carboxylic acid which enhance polymerizability of the mixture. The stereoregularity of polymers determined by NMR depended on increasing irradiation dose and temperature rather than the content of the added liquid-crystalline 4-n-decanoxybenzoic acid.     

Preparation of Micron-size Functional Fluorescent Microspheres

As a kind of special functional microspheres, fluorescent polymer microspheres could be used in cell label and separation, blood flow assay, flow cytometer marking, chemical reaction assay,and in analyst of the transform and diffusion of particles in soil 1. However, one of the most important applications of fluorescent microspheres is in the high-throughput screening of drugs (HTS) 2. Through affinity interaction, radioactive ligands (latent drugs) are bound to fluorescent microspheres covered by receptor, and luminescence is produced by radioactivity, so ligands can be assayed and screened.In this study, we developed a technique for preparing micron-size fluorescent microspheres with different functional groups. The methods included the synthesis of micron-size polystyrene microspheres through the dispersion polymerization of styrene in different media such as ethanol,ethanol-water, and isopropanol; the functional polystyrene microspheres were prepared by introduction of functional monomers into the reaction system of styrene; the functional fluorescent microspheres were obtained by the way of dying functional microspheres in the fluorescent material's ethanol solvent.The average diameter of microspheres was in the range of 1～10 μm, and the distribution was normal distribution. The functional groups included -OH, -CHO, -COOH, -CONH2, and SO3H. The absorbing spectrum and exciting spectrum were tested, the results showed that the maximal absorbance of fluorescent microsphere was near 306.5 nm, and its maximal excitation was near 362 nm. The excitation spectrum of fluorescent material (DPO) and fluorescent microspheres were shown in figure 1, and it indicated that the developed fluorescent microspheres showed the same excitation behavior like DPO, which related to the fluorescent microspheres had stable luminescence property.     

Binding studies of sodium dodecyl benzene sulphonate with poly(N-vinyl-2-pyrrolidone)

The binding of sodium dodecyl benzene sulphonate (SDBS) with poly(N-vinyl-2-pyrrolidone) (PVP) has been investigated at 303.15 and 313.15 K using equilibrium dialysis, surface tension, viscosity, ultrasound velocity and ultrasound absorption techniques. From each of these studies four distinct regions of SDBS-PVP interactions were observed. Interaction of SDBS with PVP was found to involve the binding of surfactant dimers with the polymer molecule followed by usual micellization. The binding data has been analyzed in terms of various models of polymer-surfactant interaction.     

Synthesis and cationic photopolymerization of electroactive monomers containing functional groups

The synthesis and cationic photopolymerization of different cationically polymerizable monomers containing electroactive groups are reviewed with 98 references. The preparation of various compounds containing electron‐donor or electron‐acceptor moieties and photopolymerizable functional groups is described. After a short discussion of basic principles of cationic polymerization, photoinduced cationic polymerizations of various cationically polymerizable monomers containing both electron‐donor or electron‐acceptor chromophores and the functional groups such as epoxy, vinyl, thiiranyl, oxetanyl and others are reviewed. Copyright © 2005 John Wiley & Sons, Ltd.     

Perfluorinated polymer surfaces comprising SF5-terminated long-chain perfluoroacrylate

A new perfluorinated acrylate monomer containing the SF₅(CF₂)₆-perfluorinated side chain was synthesized and polymerized into films. Bulk monomer characterization is consistent with the molecular structure based on FTIR, mass spectrometry and NMR analyses. The surface properties of polymer coatings were studied with aqueous wetting (contact angle) and X-ray photoelectron spectroscopy (XPS) methods. The surface composition is shown to be highly enriched in the terminal side chain SF₅-chemistry and exhibits properties consistent with a highly apolar, non-wetting perfluorinated polymer surface. Depth-dependent XPS studies using angular-resolved methods (ADXPS) confirmed a non-stoichiometric enrichment of sulfur and fluorine at the film ambient interface, consistent with a surface presence of the terminal SF₅-group and possibly film structural anisotropy in the surface zone. Time-of-flight (TOF) secondary ion mass spectrometry (SIMS) analysis supplements the XPS data by showing the presence of all expected SF₅-acrylate chemistry components in the outer 15 Å of the film surface.     

PABA疏水缔合水溶性共聚物溶液的合成与性能研究

本文根据高分子的分子设计原理，合成了带苯基的疏水单体N－苯基对正丁基丙烯酰胺（BBAM）。采用自由基胶束共聚的方法制备了水溶性丙烯胺／N－苯基对正丁基丙烯酰胺（BBAM）疏水缔合型共聚物（PABA）。研究了共聚物溶液的性能及影响因素。结果表明，随共聚物溶液浓度的增加，在临界缔合浓度以上，分子间缔合大量形成，水溶液表现粘度迅速增加，表现出明显的疏水缔合行为，与HPAM相比有优异的抗盐性。     

基于非生物折叠体的分子识别

利用分子自组装的方法控制大分子量的线性有机分子的构象是物理有机化学一个富于挑战性的研究课题. 近年来, 化学家已经成功利用不同的分子内非共价键作用力如氢键和疏溶剂作用等诱导线性分子的折叠乃至螺旋构象的产生. 综述了近年来这种新的非生物二级结构形式在分子识别研究中的应用.     

INTROMISSION OF WATER-REPELLENT AND HYDROSCOPIC PROPERTIES SIMULTANEOUSLY TO PP BY PLASMA DISCHARGE METHOD

Plasma-induced surface graft copolymerization of acrylic acid on polypropylene non-woven fabric (PP-g-AA) and polypropylene membrane were reported. The extents of grafting were controlled by the plasma and polymerization condition. Hexadecyltrimethyl ammonium bromide was then coupled with the carboxyl group of PP-g-AA to obtain a polyion complex (PIC). At last, CF4 plasma was used to give PICs hydrophobic property. The moisture regain and water-repellency of the processed PICs was investigated. The surfaces were characterized using ATR FT-IR and XPS. The result indicates that the products have very high ability to adsorb moisture, even better than cotton fiber. At the same time, the products show excellent hydrophobic property, which can‘t be wetted by those reagents whose surface tensions were higher than 327mN/m.     

Synthesis and polymerization of N-[N′-(α-methylbenzyl)aminocarbonyl-n-alkyl]maleimide

Two types of optically active N-[N′-(α-methylbenzyl)amino/carbonyl-n-alkyl]maleimides (MBAC) were synthesized from maleic anhydride, 6-amino-n-caproic acid (or 12-amino-n-dodecanoic acid), and (R)-(+)-α-methylbenzylamine. Radical homopolymerizations of MBAC were performed in several solvents at 60 and 110°C for 24 h to give optically active polymers. Radical copolymerizations of MBAC were performed with styrene (ST) and methyl methacrylate (MMA) in dioxane at 60°C. The monomer reactivity ratios and the Alfrey-Price Q-e values were determined. Chiroptical properties of the polymers and copolymers were investigated. © 1995 John Wiley & Sons, Inc.     

Synthesis of substituted polymethylenes by radical polymerization of alkyl N,N-dialkylfumaramates and maleamates: Relative reactivity of the isomers

Bulk polymerization of alkyl N,N-dialkylfumaramates (FAE) and maleamates (MAE) was performed in the presence of a radical initiator. It has been found that FAE is more reactive than MAE when the reactivity of the two geometrical isomers was compared for their homo- and copolymerizations. From investigation on the effect of ester and N-substituents of these monomers, it has been found that the isopropyl ester shows a higher reactivity than the methyl ester and that N-ethyl and n-butyl substitution gives polymers with high molecular weight of more than several thousands. The resulting substituted polymethylenes from FAE and MAE were characterized and compared with each other. The isomerization of MAE to FAE with morpholine as an isomerization catalyst and monomer-isomerization radical polymerization were also investigated.