棉籽油间歇式酯交换反应动力学的研究

生物柴油(棉籽油甲酯)可以由棉籽油与甲醇在催化剂KOH存在下通过酯交换反应制得。故对棉籽油间歇式酯交换反应动力学进行了研究,并考察了反应温度和催化剂浓度对产物棉籽油甲酯浓度的影响。用液相色谱法分析棉籽油的组成;用气相色谱法分析产物中棉籽油甲酯的含量。由实验数据绘制的动力学曲线得到酯交换反应在开始阶段为准二级反应,以后紧接转为一级反应和零级反应,与文献报导的棕榈油酯交换反应动力学结果一致。由实验数据求出酯交换反应在开始阶段的动力学参数,35℃、45℃时的反应速率常数分别为0.9179Lmol-1min-1和1.049Lmol-1min-1,酯交换反应的活化能为10.88kJmol-1。根据实验结果得到棉籽油酯交换反应的最佳反应温度为45℃,最佳催化剂为1.1%KOH。     

SMAS/AM/淀粉抗温接枝共聚物的研究

研究了甲基丙烯磺酸钠(SMAS)、丙烯酰胺(AM)与淀粉接枝共聚物的合成方法，接枝反应的影响因素和热稳定性。实验结果表明，该接枝反应基本符合自由基反应的一般规律，并且其聚合产物具有明显的抗高温能力。     

Rheology of poly(n‐butyl methacrylate) and its composites with calcium carbonate

Poly(n‐butyl methacrylate) (PBMA) composites with calcium carbonate (CaCO₃) were prepared by in situ radical copolymerization of butyl methacrylate (BMA) and methacrylic acid (MA) with precipitated calcium carbonate. To compare the different rheological behaviors of the monomer mixtures with CaCO₃ and the composites, the steady and dynamic viscosities of BMA/MA/CaCO₃ and poly(BMA/MA/CaCO₃) were measured by means of steady and oscillatory shear flows. The viscosity of the mixture BMA/MA/CaCO₃ was found to increase evidently with the increasing of CaCO₃%. The influence of MA% on viscosity of BMA/MA/CaCO₃ was slight. During the in situ polymerization, the viscosity of the reacting system was measured to be enhanced by a factor of about 10⁴ from the monomer/CaCO₃ mixture to composites. The dependency of zero‐shear viscosity on molar mass of PBMA was also investigated. The relation between the zero‐shear viscosity and molar mass is η₀ = 10^?15 M_w^3.5. The evolution of the viscosity with the temperature for both PBMA and its composites was obtained and time–temperature superposition was used to build master curves for the dynamic moduli. The flow activation energies were found to be 115.0, 148.6, and 178.7 kJ/mol for PBMA, composite PBMA/CaCO₃ (90/10), and PBMA/MA/CaCO₃ (89/1/10), respectively. The viscosity of the composites containing less than 10% CaCO₃ was lower than that of pure PBMA with the same molar mass. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1376–1383, 2003     

气相酯交换法合成碳酸甲丙酯负载型催化剂的研究

考察了负载型金属氧化物催化剂对碳酸二甲酯和丙醇气相酯交换合成碳酸甲丙酯的催化性能,并采用BET、XRD、CO2-TPD方法对催化剂进行了表征.结果表明,TiO2/Al2O3对反应具有较高的催化活性和稳定性.随着TiO2负载量的增加,催化剂的比表面积减小,而催化性能则随Ti负载量的增加先增加后减小,在Ti负载量为5%(wt)时活性达到最高,当Ti负载量低于5%(wt)时,TiO2可能以非晶态形式分散在Al2O3表面,而当Ti负载量高于5%(wt)时,TiO2以微晶的形式存在.CO2-TPD研究表明,负载量的改变对催化剂的碱性影响不明显.     

阳离子型丙烯酸树脂的合成及其水溶性研究

以自由基聚合法合成了阳离子型丙烯酸树脂，通过稳定性比较考察了甲基丙烯酸缩水甘油酯(GMA)用量及树脂中和度对树脂水溶性的影响，用Zeta电位研究了中和度对胶体稳定性的影响，采用激光光散射仪(LLS)测定了胶体颗粒在水分散液中的流体动力学半径及分布，研究表明：当GMA用量为15％(质量分数)，中和度为80％时．体系中胶体颗粒具有足够的亲水性和良好的稳定性。     

Controlled destruction of residual crosslinker in a silicone elastomer for drug delivery

In drug delivery systems that use silicone elastomers as a diffusion matrix for the active drug, it is common to crosslink the material by the hydrosilylation reaction. In this platinum‐catalyzed reaction, vinyl groups on a polymer add to the methyl siloxane hydride (MHS) groups on a low molecular mass crosslinker. With an excess of crosslinker, a fast curing is achieved and a fully crosslinked material is formed. Unreacted MHS groups were shown to remain in the elastomer after curing because of the excess crosslinker. In this work, a simple procedure was developed to eliminate the unreacted MHS groups from the final product. We found that storage of the product at +40°C and 75% relative humidity for a few weeks will effectively destroy the residual MHS groups in the elastomer. The effects of varying levels of humidity, oxygen, and temperature on this postcuring procedure were studied. The amount of MHS groups was measured with NMR and IR spectroscopy. We also found that the hardness of the material increased by approximately 25% as a consequence of this postcuring treatment. This increase is probably due to a secondary crosslinking reaction between MHS and silanol groups. Heat treatment at higher temperatures led to an even further increase in the hardness and compression modulus. Because no MHS groups remained in the elastomer when this heat treatment was started, it is apparent that another secondary crosslinking reaction is occurring, probably silanol condensation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2254–2264, 2002     

过氧化甲乙酮合成研究

研究了在酸性催化剂存在下，以邻苯二甲酸二丁酯作溶剂，由双氧水和甲乙酮作用制取过氧化甲乙酮溶液的工艺，并得到最佳工艺条件。结果表明，产品性能优良。     

Blends of ethylene–methyl acrylate–acrylic acid terpolymers with ethylene–acrylic acid copolymers: Mechanical and thermomechanical properties

The effect of methyl acrylate content in ethylene–methyl acrylate–acrylic acid (E–MA–AA) terpolymers and acrylic acid content in ethylene–acrylic acid (E–AA) copolymers was investigated in blends of these two materials. The E–MA–AA terpolymer with 8 mol % methyl acrylate was not miscible with any E–AA material no matter what the AA content, whereas the terpolymer with only about 2 mol % methyl acrylate was miscible, at least to some extent, with the E–AA copolymer at high acrylic acid contents. Evidence supporting this conclusion derived from gloss, differential scanning calorimetry testing, and dynamic mechanical measurements. For the E–AA polymer material with the highest acid content, there was a synergistic effect for some properties at low added amounts of E–MA–AA copolymer; the tensile strength and hardness were 10% higher than values for the E–AA copolymer, even though the E–AA copolymer was much stiffer. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2216–2222, 2004     

超支化聚酯的合成及光固化性能研究

通过甲基四氢苯酐和环氧丙醇的开环聚合反应，一步法制备超支化聚酯，聚酯的数均摩尔质量为1450～2600g／mol，支化度在0．41～0．71之间。用甲基丙烯酸缩水甘油酯改性，合成了UV固化超支化聚酯，并对其光固化性能进行了初步研究，发现超支化聚酯能有效降低固化膜的线收缩率，聚酯的官能度越高，固化膜的硬度越大，固化速度越快，在约1s的固化时问内凝胶率超过75％。     

Friction and adsorption properties of normal and high-oleic soybean oils

The steel/steel boundary friction properties of soybean oil (SBO) and high-oleic soybean oil (HOSBO) are compared. HOSBO is significantly more saturated than SBO and more oxidatively stable. Changes in degree of unsaturation affect lateral interactions of adsorbate molecules, which in turn affects their adsorption and, hence, their boundary lubrication properties. To investigate this possibility, the free energies of adsorption (ΔG _ads) of SBO, HOSBO, and methyl laurate (ML) were determined from the analysis of friction-derived adsorption isotherms using the Langmuir and Temkin adsorption models. The results showed a stronger adsorption for the vegetable oils than for ML, an indication of multiple interactions between the ester groups of the triglycerides and the steel surface. The result also showed no difference in the ΔG _ads values of SBO and HOSBO obtained using either the Langmuir or Temkin models. This was interpreted as an indication of the lack of appreciable net lateral interaction between triglyceride adsorbates.