羧基丙烯酸酯涂料合成及其防雾性能研究

采用种子乳液聚合法合成了一种互穿网络型羧基丙烯酸酯类聚物乳液，研究了加料方式对羧基分布的影响，结果表明丙烯酸加入到核单体中有利于羧基分布在乳胶粒表面。在体系中引入离子键交联结构提高了乳液涂料的硬度和耐水性能，离子键交联ＰＩＬＮ型涂料具有优良的防雾性能。     

Thermal transitions and fat droplet stability in ice-cream mixmodel systems

We studied thermal transitions and physical stability of oil-in-water emulsions containing different milk fat compositions, arising from anhydrous milk fat alone (AMF) or in mixture (2:1 mass ratio) with a high melting temperature (AMF–HMT) or a low melting temperature (AMF–LMT) fraction. Changes in thermal transitions in bulk fat and emulsion samples were monitored by differential scanning calorimetry (DSC) under controlled cooling and reheating cycles performed between 50 and –45°C (5°C min^–1). Comparison between bulk fat samples and emulsions indicated similar values of melting completion temperature, whereas initial temperature of fat crystallization (T_onset) seemed to be differently affected by storage temperature depending on triacylglycerols (TAG) composition. After storage at 4°C, T_onset values were very similar for emulsified and non-emulsified AMF–HMT blend, whereas they were lower (by approx. 6°C) for emulsions containing AMF or mixture of AMF–LMT fraction. After storage at –30°C, T_onset values of re-crystallization were higher in emulsion samples than in bulk fat blends, whatever the TAG fat composition. Light scattering measurements and fluorescence microscopic observations indicated differences in fat droplet aggregation-coalescence under freeze-thaw procedure, depending on emulsion fat composition. It appeared that under quiescent freezing, emulsion containing AMF–LMT fraction was much less resistant to fat droplet aggregation-coalescence than emulsions containing AMF or AMF–HMT fraction. Our results indicated the role of fat droplet liquid-solid content on emulsion stability.     

Preparation of high molecular weight polyurethane particles by nonaqueous emulsion polyaddition

A versatile nonaqueous emulsion polyaddition process for the one-step fabrication of spherical polyurethane nanoparticles is presented. Three different emulsion systems were used consisting of N,N′-dimethylformamide (DMF) dispersed in n-hexane, acetonitrile dispersed in cyclohexane, and acetonitrile dispersed in tetradecane. After successful stabilization of the emulsion systems by using a poly(isoprene)-poly(methylmethacrylate) block copolymer, the fabrication of the polyurethanes was carried out within the dispersed polar phase. The polyurethane particles showed average diameters as small as 35 nm. Additionally, infrared (IR) characterization revealed that the formation of any urea, which decreases the mechanical properties of the polyurethanes, was prevented during the polyaddition. This was attributed to the anhydrous reaction conditions. Gel permeation chromatography (GPC) analysis demonstrated the average molecular weights (M _n) of the polyurethanes to be as high as 16,500 g/mol, corresponding to conversions of 0.98. Comparable molecular weights and conversions have not previously been achieved without the formation of urea.     

Monodisperse thermosensitive particles prepared by emulsifier-free emulsion polymerization with microwave irradiation

The emulsifier-free emulsion polymerization of styrene (St) and N-isopropylacrylamide (NIPAAm) was successfully carried out with microwave irradiation, and the monodisperse thermoresponsive poly(styrene-co-N-isopropylacrylamide) (poly(St-co-NIPAAm)) particles with diameters in the range 100–130 nm were prepared. The morphology, size and size distribution of the poly(St-co-NIPAAm) particles were characterized by transmission electron microscopy, scanning electron microscopy (SEM) and photon correlation spectroscopy (PCS), respectively. The results showed that poly(St-co-NIPAAm) particles had spherical morphology, and the poly(St-co-NIPAAm) particles prepared by emulsifier-free emulsion polymerization with microwave irradiation were smaller, more uniform than those obtained with conventional heating. The hydrodynamic diameters of poly(St-co-NIPAAm) particles were decreased as the temperature increased from 25 °C to 40 °C, and poly(St-co-NIPAAm) particles collapsed remarkably at 32 °C, which is the lower critical solution temperature of the poly(N-isopropylacrylamide). The morphology of the assembled poly(St-co–NIPAAm) particles was observed by SEM, it was found that monodisperse poly(St-co-NIPAAm) particles could assemble to form the two-dimensional order structures.     

γ辐照引发无皂乳液聚合法一步合成Ag-聚4-乙烯基吡啶杂化微凝胶

无机-聚合物纳米复合材料是将聚合物与一种或多种无机纳米粒子复合而成的一种材料,它同时具有无机纳米粒子和聚合物的优良特性,在许多重要技术领域具有广泛的应用前景.近20年来,无机-聚合物纳米复合材料的制备及应用备受关注[1~6].包括杂化微凝胶在内的纳米复合微球是无机-聚合     

A novel way to study the initial stages of soap-free emulsion polymerizations: The intercalation of polystyrene oligomers into hydrotalcite

The dominant species in the early stages of an emulsifier-free emulsion polymerization of styrene has been found to be an oligomer of two to three monomer units using a novel trapping technique. This involved the intercalation of charged primary oligomers between the layers of a hydrotalcite, [Mg₄Al₂(OH)₁₂]²⁺[A]^2- (where A = dianion). Hydrotalcites are an important class of lamellar, inorganic compounds whose interlayer spacing can be mod-ified by anion exchange. Our approach first involved preparing a hydrotalcite precursor in which the layers were propped apart by an organic dianion (terephthalate = TA). This material was then used to capture the negatively charged polystyrene oligomers from the emulsion polymerization reaction mixture. We found that TA was rapidly ion-exchanged for the charged oligomers. The resulting pillared hydrotalcite material was characterized using XRD and SEC. We found that the interlayer spacing between the hydroxide layers increased to 23.2 Å on exposure to the emulsion reaction mixture. This represents an interlayer expansion of 18.3 Å (after subtraction of the hydroxide layer contribution), which is cnsistent with intercalation of oligomers with two to three monomer units arranged in a bilayer. This size estimate was confirmed by the results of size exclusion chromatography. © 1995 John Wiley & Sons, Inc.     

氧化-还原低温引发甲基丙烯酸甲酯/丙烯酸丁酯超浓乳液聚合研究

以乳化剂十二烷基硫酸钠 (SDS)和共乳化剂十六烷醇 (HD)作为复合乳化体系 ,过氧化二苯甲酰(BPO)和N ,N 二甲基苯胺 (DMA)作为氧化还原引发体系 ,甲基丙烯酸甲酯 丙烯酸丁酯 (MMA BA)作为混合单体 ,制备了分散相占 83 %以上的稳定的超浓乳液 ,然后在低温下引发聚合 .探讨了引发剂浓度、氧化剂与还原剂的摩尔比、乳化剂的浓度、液膜增强剂的种类、聚合温度等因素对聚合稳定性和聚合速率的影响 ,测定并计算得到了聚合速率的公式 ;用激光散射粒度分布仪测定了聚合物乳胶粒子的大小及粒径分布 ,用透射电子显微镜观察了聚合物乳胶粒的形态 ,讨论了乳化剂浓度、聚合温度等对乳胶粒形态、大小的影响     

Kinetic and stability characterization ofChromobacterium viscosum lipase and its comparison withPseudomonas glumae lipase

A kinetic study ofChromobacterium viscosum lipase was undertaken, and compared withPseudomonas glumae lipase. Optimum operation conditions were pH 9.0 and 50°C for both enzymes. A substrate specificity study was also developed. Both enzymes showed higher activity on triglycerides with a long chain of fatty acid; the specific activity was always higher for C.viscosum lipase. Stability of both enzymes in aqueous medium at 60°C and pH 9.0 was evaluated. C.viscosum lipase was three times more stable than P.glumae lipase, with at _1/2 value of 0.75 h. In addition, the activity of C.viscosum lipase with substrate concentration was studied with a triolein emulsion. A dependence of the intrinsic characteristics of the emulsion was observed. Therefore, stability ofC. viscosum lipase B with reaction products was assayed in a micellar system. Acid products reduced the specific activity of the enzyme. Glycerol and high buffer concentration were stabilizers of enzyme deactivation. Finally, substrate specificity ofC. viscosum lipase B in a micellar system was developed with tributyrin, tricaprylin, and triolein. Only tributyrin showed an apparent Michaelis-Menten kinetic with V_max ^app = 958 U/mg and K_ma ^app = 75.5 mM. Tricaprylin and triolein showed diffusion limitations at low substrate concentration and substrate inhibition at high substrate concentration. Diffusion parameters were calculated for both these substrates. Mass transfer coefficients (k₁) were 0.314 Å/min and 1.53 Å/min for tricaprylin and triolein, respectively. Effectiveness factors (η) were 0.536 and 0.768 for tricaprylin and triolein, respectively.     

Compartmentalized polymerization initiated by oil-soluble initiators. Calculation of average number of radicals per particle

Expressions for calculating the stationary state distribution of radicals in compartmentalized systems with a constant number of reaction loci containing an oil-soluble initiator are given. Besides pairwise formation of radicals in the particles, desorption and reabsorption, water phase termination, solubility of the initiator in the aqueous phase, and the possibility of formation of a single radical species are taken into consideration. The calculation is based on a probabilistic analysis leading to a third-order recurrence relation solved using confluent, hypergeometric Kummer functions. Some calculated curves illustrating the de-pendence of the average number of radicals per particle on various relevant parameters are included. © 1995 John Wiley & Sons, Inc.     

A competitive particle nucleation mechanism in the polymerization of homogenized styrene emulsions

The effects of concentrations of surfactant (sodium lauryl sulfate [SLS]) and initiator (sodium persulfate [SPS]) on the polymerization of homogenized styrene emulsions, stabilized by SLS/lauryl methacrylate (LMA) or SLS/stearyl methacrylate (SMA), were studied. The rate of polymerization increases with increasing [SLS] or [SPS]. In addition to monomer droplet nucleation, the formation of particle nuclei in the aqueous phase (homogeneous nucleation) plays a crucial role in the polymerization kinetics. In comparison with the LMA containing polymerization system, monomer droplet nucleation becomes more important when the more hydrophobic SMA was used as the costabilizer. Furthermore, the degree of homogeneous nucleation increases with increasing [SPS].