FTIR investigation of ethylene coordination and polymerization on reduced Cr/SiO2 catalyst

FTIR spectroscopy was applied to study the initial steps of ethylene polymerization on reduced chromia-silica (0.5 wt% Cr/SiO₂). To decrease the speed of the reaction small doses of gas were introduced to the catalyst in each run and C₂D₄ was used to confirm band assignments. At the initial steps of the reaction only ethylene molecules coordinated to probably Cr _A ²⁺ cations were observed. The concentration of such complexes was estimated to be about 50% of the total amount of Cr atoms in the sample. The FTIR spectrum of the polymer formed at the initial doses of C₂H₄ (when [C₂H₄] [Cr]) was found to be slightly different from that formed after excess ethylene was introduced onto the catalyst ([C₂H₄] > [Cr]).     

Properties of poly(n‐butyl methacrylate) prepared by reverse atom transfer radical polymerization in an aqueous dispersed system

Reverse atom transfer radical polymerization (ATRP) of n‐butyl methacrylate (BMA) in waterborne media using Cu(II) complexes with azo initiators (i.e., reverse ATRP) was conducted. The influence of several factors, such as surfactant, catalyst, and reaction time, on the stability of the emulsion, the particle size, the morphology of the emulsion particles, and the control of the polymerization was investigated. The results showed great differences between ATRP and conventional emulsion polymerization, especially the nucleation mechanism and the kinetics. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1542–1547, 2003     

High solids content emulsions. III. Synthesis of concentrated latices by classic emulsion polymerization

Two different methods of producing bi‐ and trimodal latices of a mixture of methyl methacrylate, butyl acrylate, and small amounts of acrylic acid were tested. It is shown that a combination of concentrating blends of seed particles by semibatch reaction, followed by a nucleation of small particles plus a second semibatch phase allowed us to obtain stable latices with solids contents over 65% and viscosities of below 2500 mPa s^?1 with little coagulum formation. The key parameter in determining latex stability, coagulum formation, and viscosity appears to be the the particle size distribution, and especially its modification attributed to secondary nucleation. Because it is not possible to eliminate water‐soluble monomers from the polymerization recipe, secondary (homogeneous) nucleation must be minimized by careful addition of the free‐radical initiator and choice of monomer feed flow rates. The nucleation of the third population in the trimodal latices is best accomplished with a mixed surfactant system because renucleation by anionic surfactant alone leads to detrimental changes in the particle size distribution (PSD) resulting from excessive flocculation of particles. In addition, it was found that the viscosity of the final products was not sensitive to small changes in the ionic strength of the latex, although neutralization to a pH of 6 effectively doubles the final latex viscosity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1916–1934, 2002; DOI 10.1002/app.10513     

Poly(butylene terephthalate)/organoclay nanocomposites prepared by in situ interlayer polymerization and its fiber (II)

Intercalated nanocomposites with poly(butylene terephthalate) (PBT) incorporated between the montmorillonite layers were synthesized from dimethyl terephthalate and 1,4-butane diol by using an in situ interlayer polymerization. The PBT nanocomposites were melt-spun at different organoclay contents to produce monofilaments. The samples were characterized by using wide angle X-ray diffraction, electron microscopy, thermal analysis, and tensile testing. The extent of the clay layer in the PBT was confirmed by using X-ray diffraction and electron microscopy, and the clay layer was found to be highly dispersed on a nanometer scale. The addition of only a small amount of organoclay was enough to improve the thermo-mechanical properties of the PBT hybrid fibers. The hybrids were extruded with various draw ratios (DRs) to examine the tensile mechanical property of the fibers. At DR=1, the ultimate tensile strength of the hybrid fibers increased with the addition of clay up to a critical content and then decreased. However, the initial modulus monotonically increased with increasing amount of organoclay in the PBT matrix. When the DR was increased from 1 to 6, for example, the strength and the initial modulus values of the hybrids containing 3 wt% organoclay decreased linearly.     

悬浮法合成聚丙烯腈高吸水性树脂

以偶氮二异丁腈为引发剂，用悬浮聚合法合成了交联聚丙烯腈，然后对其进行水解，得到了高吸水性聚丙烯腈。交联剂用量和水解条件对树脂吸水倍数的影响很大。树脂吸去离子水倍数为420倍，平均粒径为250μm。     

Olefins polymerization on titania and titania-supported rhodium

The adsorption of ethene and propene on titania and titania-supported rhodium has been studied, observing a continuous adsorption even after 24 h. The samples have been reduced at 623 or 773 K, but no difference was observed, whichever the reduction temperature or the presence of rhodium, on the amount of gas adsorbed per unit of surface area of the solid. A study of the polymerization has been done following the equal reactivity hypothesis, and it has been concluded that the role played by the rhodium particles is to facilitate adsorption of the gaseous molecule, that is then transfered to the surface of the support, where it polymerizes.     

IR study of the interaction of hydroxyl groups of silica gel with Cr species of Phillips' type catalysts

Spectroscopic evidence for the interaction of hydroxyl groups and chromium ions was obtained using a catalyst prepared from chromyl chloride. A new OH peak, observed at 3705 cm^–1 after pumping away CO gas, is attributed to the direct interaction of OH with the low-valent chromium. This peak shifts to 3590 cm^–1 on contact with O₂ at room temperature and it is assigned to a hydroxyl interacting with the oxidized chromium. New assignments are also proposed for IR bands of CO presorbed on the catalyst. The peak due to CO at 2188 cm^–1 decreases as the OH intensity at 3705 cm^–1 increases, suggesting that the former peak arises from adsorption on Cr(II) species to which two oxygen atoms are attached.     

通过细乳液聚合方法制备自交联型有机硅乳液

苯乙烯与甲基丙烯酸-3-三甲氧基硅丙酯(M PS)经细乳液聚合,制得了稳定的自交联型的水分散涂料,用透射电子显微镜(TEM)、动态光散射仪(DLS)和红外光谱(IR)表征了乳胶粒的形态和结构。发现与传统乳液聚合相比,细乳液聚合法可显著提高乳液的稳定性,且M PS加入量的增加会导致乳液稳定性降低。     

溶液缩聚物分子量分布及其控制的研究

本文根据溶液缩聚基本原理及反应过程的基本事实，用随机过程方法，得到缩聚产物分子量分布函数，并对分子量及其分布的控制作了讨论。     

石蜡聚苯乙烯微球的制备

通过悬浮聚合技术合成了石蜡聚苯乙烯微球，研究了合成过程中引发剂浓度及交联剂用量对微球粒径及其分布的影响。