Does morphology stick? Tailored particle morphologies by swelling polymerization process

Structured dispersion particles suitable for pressure sensitive adhesives (PSA) were synthesized via swelling polymerization technique (EP 359562). Particles consisting of poly(n‐butyl acrylate) copolymerized with different types of carboxylic acids were used as seeds. The final particles were synthesized by swelling polymerization process, using 6 wt % styrene or 6 wt % methyl methacylate. The resulting particle morphology was analyzed by atomic force microscopy (AFM) and transmission electron microscopy (TEM). From previous works (Coll Surf A 2001, 183–185, 725–737; J Appl Polym Sci 2004, 91, 2610–2623) where two‐step emulsion polymerization was used on similar particles, it is expected that the particle morphology is affected by the polarity of the monomer used for swelling polymerization because of the phase compatibility (thermodynamic parameter). In this work, the seed particles used were always of a glass transition temperature (T_g) below polymerization temperature. The diffusion of the growing polymer chains from the swelling polymerization is therefore mainly affected by their own T_g and the influence of the carboxy groups on the chain length of the entering radicals (kinetic parameter). The different morphologies of the single particles are discussed qualitatively. The effects of reaction parameters are compared with the results given in the previous work. The structure of the corresponding dispersion films was characterized using AFM. Correlations to macroscopic properties such as the cohesive strength and peel adhesion to different substrates are discussed. The results are also compared with the application properties of the corresponding unmodified particles, statistical copolymers, and to blends with small sized PMMA or PS particles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1444–1455, 2006     

Polymerization of liquid propylene with a fourth‐generation Ziegler–Natta catalyst: Influence of temperature,hydrogen, monomer concentration,and prepolymerization method on powder morphology

Liquid propylene was polymerized in a 5‐L autoclave batch reactor using a commercially available TiCl₄/MgCl₂/Al(ethyl)₃/DCPDMS Ziegler–Natta catalyst, with a phthalate ester as internal electron donor. The powders from these polymerizations were characterized using laser diffraction particle size distribution (PSD) analysis, scanning electron microscopy (SEM), and bulk density measurements. These characteristics were analyzed as a function of the process conditions, including hydrogen and monomer concentration, polymerization temperature, and the prepolymerization method. It was shown that polymerization temperature influences the powder morphology to a large extent. At low temperatures, high‐density particles were obtained, showing regular shaped particle surfaces and low porosities. With increasing temperature, the morphology gradually was transferred into a more open structure, with irregular surfaces and poor replication of the shape of the catalyst particle. When using a prepolymerization step at a relatively low temperature, the morphology obtained was determined by this prepolymerization step and was independent from conditions in main polymerization. The morphology obtained was the same as that observed after a full polymerization at temperature. Even when using a short polymerization at an increasing temperature, the morphology was strongly influenced by the initial conditions. The effect of variation in hydrogen concentration supported the conclusion that the initial polymerization rate determines the powder morphology. In the absence of hydrogen, high bulk densities, and regularly shaped particles were obtained, even at high temperatures. With increasing hydrogen concentration, the reaction rates increased rapidly, and with that changed the morphology. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1421–1435, 2003     

影响纳米CeO_2晶粒形貌的因素及机理

以Ce(NO3)3.6H2O为铈源,NH3.H2O为沉淀剂,用普通沉淀法在不同反应条件下制备了粒径、形貌各异的纳米CeO2。研究结果表明,Ce(NO3)3最佳浓度为0.2 mol/L。XRD和IR结果证实了产物的物相结构。TEM分析表明:控制pH可以得到形貌不同的纳米CeO2粒子。用乙醇作溶剂得到了粒径约为15 nm、分布均匀的纳米CeO2颗粒。正加料(沉淀剂滴入盐溶液中)可以得到各种形貌的纳米CeO2;而反加料(盐溶液滴入沉淀剂中)仅能得到针状纳米CeO2颗粒。     

核壳型乳液聚合研究进展

综述了近年来核/壳结构聚合物乳液的聚合工艺、性能及核/壳结构的表征方法进行,讨论了影响核/壳结构聚合物乳胶粒子形态的各种因素。     

Physical properties of polycaproamide/cationic dyeable poly(ethylene terephthalate) polyblended fibers

Polycaproamide (PCA) and cationic dyeable poly(ethylene terephthalate) (CDP) polymers were blended mechanically (in ratios of 75/25, 50/50, and 25/75) in a melt twin‐screw extruder to prepare three PCA/CDP polyblended materials. The blends of PCA and CDP were spun into fibers. The molar ratio of dimethyl 5‐sulfoisophthalate sodium salt for CDP was 2%. This study investigated the physical properties of PCA/CDP polyblended fibers with nuclear magnetic resonance, gel permeation chromatography, gas chromatography, potentiometer, differential scanning calorimetry (DSC), thermogravimetric analysis, scanning electron microscopy (SEM), extension stress–strain measurements, density gradient analysis, and rheometry. The experimental results of DSC proved that PCA and CDP formed an immiscible system. In an SEM image of a 50/50 PCA/CDP blend, the morphological aggregation of a larger size, from 3 to 5 μm in diameter, was observed. The rheological behavior of the PCA/CDP polyblended materials exhibited negative‐deviation blends, and the 50/50 blend of the PCA/CDP polyblended fibers showed a minimum tenacity value. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1710–1715, 2004     

Synthesis and characterization of new functional poly(urethane‐imide) crosslinked networks

To synthesize new functional poly(urethane‐imide) crosslinked networks, soluble polyimide from 2,2′‐bis(3,4‐dicarboxyphenyl) hexafluoropropane dianhydride, 4,4′‐oxydianiline, and maleic anhydride and polyurethane prepolymer from polycaprolactone diol, tolylene 2,4‐diisocyanate and hydroxyl ethyl acrylate were prepared. Poly(urethane‐imide) thin films were finally prepared by the reaction between maleimide end‐capped soluble polyimide (PI) and acrylate end‐capped polyurethane (PU). The effect of polyurethane content on dielectric constant, residual stress, morphology, thermal property, and mechanical property was studied by FTIR, prism coupler, Thin Film Stress Analyzer (TFSA), XRD, TGA, DMTA, and Nano‐indentation. Dielectric constant of poly(urethane‐imide) thin films (2.39–2.45) was lower than that of pure polyimide (2.46). Especially, poly(urethane‐imide) thin films with 50% of PU showed lower dielectric constant than other poly(urethane‐imide) thin films did. Lower residual stress and slope in cooling curve were achieved in higher PU content. Compared to typical polyurethane, poly(urethane‐imide) thin films exhibited better thermal stability due to the presence of the imide groups. The glass transition temperature, modulus, and hardness decreased with increase in the flexible PU content even though elongation and thermal expansion coefficient increased. Finally, poly(urethane‐imide) thin films with low residual stress and dielectric constant, which are strongly affected by the morphological structure, chain mobility, and modulus, can be suggested to apply for electronic devices by variation of PU. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 113–123, 2006     

纳米碳酸钙的制备及表征

研究了以氧化钙和二氧化碳为原料,化学法制备纳米碳酸钙的工艺条件、添加剂的影响及形态。结果表明:中间体氢氧化钙的初始浓度、二氧化碳的流量、反应温度、搅拌速度及添加剂等在控制制备纳米碳酸钙颗粒的形状和尺寸中均十分重要。透射电镜观察结果表明:通过控制反应及添加剂,可以得到尺寸规整的链锁形、纺锤形和球形纳米碳酸钙。表面能谱证实产品为高纯的碳酸钙。X射线衍射和电子衍射的结果进一步表明:所制纳米碳酸钙均属方解石型六方晶系,a0=0.498 9 nm,c0=1.706 2 nm;为多晶结构。     

Epoxy-Polysulfone Networks as Advanced Matrices for Composite Materials

Compatibility between polysulfone (PSF) and epoxy oligomers in the melt state as well as the morphology and properties of alloys obtained were studied as a function of composition. The compatibility depends on the length and structure of epoxy molecules, and is best in the case of epoxysulfone oligomers (ESO).

The properties of hybrid matrices are determined by their composition and morphology. The most pronounced effects are observed in the regions of small concentrations of either component. A small quantity of PSF significantly improves thermal stability and heat resistance of the epoxy resin as well as its impact strength. On the other hand, on addition to PSF of small amounts of epoxysulfone oligomers, the processability of the matrix can be substantially improved. In particular, the melt viscosity decreases, and wetting and impregnation of fibrous reinforcement is facilitated. Besides, the matrix adhesion to fibers is increased.

Powdered PSF/ESO/curing agent mixtures are good for application in solvent-free technological processes of fibrous composites production, e.g. in electrostatic deposition of matrix particles onto a reinforcing fabric. Plastics based on hybrid matrices are distinguished by improved strength.     

Catalytic characteristics of various rubber-reinforcing carbon blacks in decomposition of methane for hydrogen production

Carbon black has recently been reported to act as an effective catalyst for methane decomposition and to exhibit stable catalytic behavior despite carbon deposition, and thus it can be used for CO₂-free production of hydrogen from natural gas. In this work, various carbon blacks with different primary particle size were investigated with respect to methane decomposition under atmospheric pressure from 1123 to 1223 K. Catalytic characteristics, such as activity, activation energy and reaction order, were investigated and compared. It was observed that with decreasing primary particle size (or increasing specific surface area), the specific activity increased and the activation energy decreased. The reaction orders for various pelletized, rubber-reinforcing carbon blacks were 0.6–0.7, about the same regardless of the primary particle size, while they were near 1 for fluffy carbon blacks. Fluffy carbon black showed higher activity and activation energy than the pelletized carbon black of the same primary particle size. Changes of the surface morphology during carbon deposition were observed by TEM. Variations of the number of active sites were discussed in regard of the primary particle size, carbon deposition and binder. The presence of different types of active sites was also suggested.     

Synthesis and characterization of thermosensitive composite microsphere latex

Monodisperse aqueous latex dispersions, prepared from mixtures of styrene, N‐isopropylacrylamide, and N,N′‐methylenebisacrylamide, were characterized. Thermosensitive composite microspheres with diameters greater than 1.0 μm, consisting of a polystyrene core and a poly(N‐isopropylacrylamide) shell, were prepared. The morphology of the composite microspheres was observed with transmission electron microscopy, and the particle size of the composite microspheres was estimated with dynamic light scattering. The thermosensitive properties of the composite microspheres were evaluated via the hydrodynamic size of the composite microspheres. The particle size of the composite microspheres decreased with increasing temperature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 824–828, 2005