Small‐angle X‐ray scattering study of modified porous suspension–poly(vinyl chloride) particles

Small‐angle X‐ray scattering (SAXS) was applied to investigate the microstructure of unmodified and modified porous commercial suspension‐type poly(vinyl chloride) (PVC) particles. The modified PVC particles were prepared by an in situ stabilizer‐free polymerization/crosslinking of particles absorbed with a monomer/crosslinker/peroxide solution. The modifying polymers include styrene with or without divinyl benzene (DVB) as a crosslinker and methyl methacrylate (MMA) with or without ethylene glycol dimethacrylate (EGDMA) as a crosslinker. The SAXS method was used to highlight the effect of polystyrene (PS) on the microstructure of PVC particles and to evaluate the characteristic lengths, both in the PVC/PS and the PVC/XPS (PS crosslinked with 0 and 5% DVB, respectively) systems. A model is suggested, where during the synthesis modification process, swelling of PVC by styrene and styrene polymerization occur simultaneously. PVC swelling by styrene causes destruction of the PVC subprimary particles, whereas styrene polymerization leads to phase separation resulting from incompatibility of the polymers. It was further suggested that because of PVC swelling by styrene, structure of the subprimary particles is lost. Therefore the characteristic lengths of PVC/PS and PVC/XPS, as calculated from the SAXS measurements, were attributed to the size of the phase‐separated PS and XPS inclusions, respectively. The SAXS method also shows that PMMA and XPMMA do not influence the PVC microstructure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1024–1031, 2005     

Solid-state NMR studies on phase behavior and motional mobility in binary blends of polystyrene and poly(cyclohexyl methacrylate)

The phase behavior and motional mobility in binary blends of polystyrene (PS) and poly(cyclohexyl methacrylate) (PCHMA) have been investigated by solid state ¹³C NMR techniques. The blend miscibility has been studied by examining the ¹H spin-relaxation times in the laboratory frame (T₁^H) and in the rotating frame (T_1ρ^H) for the PCHMA/PS blends with various compositions and pure components. The T_1ρ^H results show that PCHMA and PS are intimately mixed at the molecular level within the blends at all compositions. In addition, according to the results of carbon T_1ρ relaxation time measurements, we conclude that mixing is intimate enough to cause a reduction in local chain mobility for PS, but an increase in side chain mobility for PCHMA.     

Physical agglomeration behavior in preparation of cellulose‐N‐methyl morpholine N‐oxide hydrate solutions by simple mixing

The different melting temperatures of N‐methyl morpholine N‐oxide (NMMO) hydrates in the cellulose–NMMO hydrate solution may be explained by the rather different crystal structures of NMMO hydrates, which are determined by the amount of the hydrates. The preparative process of cellulose–NMMO hydrate solution may result in cellulose structural change from cellulose I to cellulose II, depending on the amount of the hydrate. Mixtures of cellulose and NMMO hydrate in a blender was changed from the granules to slurry with increasing mixing time at 60–70°C, which is below the melting point of the NMMO hydrate. In the case of 15 wt % cellulose–NMMO hydrate granules, which were made by mixing for 20 min, the melting points of various NMMO hydrates were obtained as 77.8°C (n = 0.83), 70.2°C (n = 0.97), and 69.7°C (n = 1.23), respectively, depending on the hydrate number. However, the melting points of cellulose–NMMO hydrate slurry and solution were shifted lower than those of cellulose granules, while the mixing time of slurry and solution are 25 and 35 min, respectively. These melting behaviors indicate instantaneous liquefaction of the NMMO hydrate and the diffusion of the NMMO hydrate into cellulose during mixing in a blender. When cellulose was completely dissolved in NMMO hydrate, the crystal structure of cellulose showed only cellulose II structure. In the cellulose–NMMO products of granules or slurry obtained by high‐speed mixing, which is a new preparation method, they still retained the original cellulose I structure. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1687–1697, 2004     

Kinetic and molecular weight control for methyl methacrylate semibatch polymerization. II. Open control

The gel effect will bring a violent increase of conversion for methyl methacrylate (MMA) polymerization in a short time. It will be very dangerous for the reactor, as it causes an increase of molecular weight and broadens the molecular weight distribution. To unify the kinetics, molecular weight, and its distribution, on the basis of the mathematical models for semibatch polymerization of MMA, three controlled objectives that are the heat load distribution index, the change in molecular weight, and molecular weight distribution index are presented. Three materials (monomer, solvent, and chain transfer agent) and their flow rate and feeding mode are analyzed for the open control of kinetics, molecular weight, and its distribution. The optimum flow rate and mode are obtained. The heat load distribution index and molecular weight distribution index are even less than 2.0 and 2.2, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4399–4405, 2006     

处理温度对锐钛型TiO2光催化活性的影响及利用可见光降解甲基紫

高温处理锐钛型TiO2可以使其转晶以改变晶型比例,因此加热温度和加热时间是影响TiO2光催化活性的主要因素.本研究中,以该方法得到了可利用可见光的TiO2催化剂,并进行了可见光降解甲基紫的研究.结果表明,在TiO2和可见光共同作用下,甲基紫的光降解效果明显优于单独使用锐钛型、金红石型和按照转晶的比率混合的锐钛型和金红石型TiO2.5.0小时的照射其降解率即可达到94.2%以上.而相同条件下,采用锐钛型、金红石型和按照转晶的比率混合的锐钛型和金红石型TiO2降解率分别只有55.82%、51.20%和40.47%.     

制备条件对二氧化钛光催化活性的影响

以钛酸丁酯为原料，采用溶胶-凝胶法制备了粉末二氧化钛催化剂，讨论了不同条件如：钛酸丁酯的浓度、加水量、陈化时间、陈化温度、焙烧时间和温度等条件对光催化降解偶氮染料甲基橙活性的影响和机理。试验结果表明：此催化剂有高的催化活性。     

微波促进二氯菊酸甲酯的水解新工艺研究

采用微波技术对二氯菊酸甲酯在NaOH溶液中水解为二氯菊酸工艺进行了研究。结果表明,微波促进下最佳水解条件为:反应温度90℃,功率100 W,反应时间10 m in,物质的量比n(二氯菊酸甲酯)∶n(C2H5OH)∶n(NaOH)=1∶4∶1.5,重结晶后收率高达99.6%。与传统条件相比,时间缩短30倍,收率提高24.6%,无水乙醇用量减少60%,NaOH用量减少17%。并用红外光谱和熔点对二氯菊酸进行表征。     

精对苯二甲酸装置乙酸甲酯回收与利用

介绍了精对苯二甲酸装置对二甲苯氧化反应过程中副产物乙酸甲酯回收与利用，乙酸甲酯回收不仅可以减少排放到大气和污水中的有机物，而且可以返回到氧化反应系统，改善反应状况，降低醋酸消耗。     

Interpenetrating polymer networks based on polyol modified castor oil polyurethane and poly(2‐ethoxyethyl methacrylate): Synthesis,chemical, mechanical,thermal properties,and morphology

Interpenetrating polymer networks (IPNs) of glycerol modified castor oil polyurethane (GC‐PU) and poly(2‐ethoxyethyl methacrylate) poly(2‐EOEMA) were synthesized using benzoyl peroxide as initiator and ethylene glycol dimethacrylate (EGDM) as crosslinker. GC‐PU/poly (2‐EOEMA) interpenetrating polymer networks were obtained by transfer molding. The novel GC‐PU/poly (2‐EOEMA) IPNs are found to be tough films. These IPNs are characterized in terms of their resistance to chemical reagents thermal behavior (DSC, TGA) and mechanical behavior, including tensile strength, Young's modulus, shore A hardness, and elongation. The morphological behavior was studied by scanning electron microscopy. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1029–1034, 2004     

Graft copolymerization of 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid onto carboxymethylcellulose (sodium salt) by H2O2/Fe+2 redox pair

The effect of the reaction conditions on the grafting parameters during grafting of 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid onto sodium carboxymethylcellulose using H₂O₂/Fe⁺² redox pair are studied at 30°C. The grafting ratio, add on, and conversion initially increase with the H₂O₂ concentration in the range of (10.0–15.0) × 10^?2 mol dm^?3. Thereafter, these parameters decrease with the H₂O₂ concentration. The grafting ratio, add on, and conversion increase when increasing the ferrous ion concentration from (0.5 to 4.0) × 10^?2 mol dm^?3 and decrease with a further increase in the concentration. It is observed that the grafting ratio and add on increase with the monomer concentration, whereas the conversion decrease. The hydrogen ions seem to be facilitating the grafting reaction up to a certain concentration and after this concentration seem to be retarding the process. The grafting ratio, add on, and conversion decrease with the sodium carboxymethylcellulose concentration. When increasing the time period from 60 to 90 min, the grafting parameters increase but decrease thereafter. Similarly, when increasing the temperature from 25 to 30°C, the grafting parameters increase and decrease thereafter. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4819–4825, 2006