合成二甲基二氯硅烷的铜系催化剂的制备及评价

本文详细论述了含Cu/CuO/Cu2O的三元铜催化剂的制备方法。以硫酸铜为原料,经脱水干燥、还原等步骤,采用部分氧化工艺制成。之后用直接法在φ32mm流化床反应器中用该催化剂合成二甲基二氯硅烷,并进行实验评价。实验结果表明该催化剂具有较高的反应产率和选择性。进一步的对铜系催化剂的粒径分布、寿命、形貌进行分析,为工业化生产提供一定基础数据。     

甲基氯硅烷单体合成反应中CuCl催化剂改性研究

针对甲基氯硅烷单体直接合成反应,提出了一种采用甲基三氯硅烷(M1)对CuC l催化剂改性的新方法。由湿法制备的CuC l催化剂表面具有大量的羟基,通过M1改性后,采用红外光谱表征,其表面羟基大幅度减少。采用反应热重的实验方法对CuC l和硅粉共同形成活性中心的反应进行了评价,结果表明改性后的催化剂能够降低形成活性中心的引发温度,为评价单体合成反应找到了一种更为简便的方法。甲基氯硅烷合成反应评价装置上的催化反应结果表明,使用改性后的CuC l催化剂,反应活性提高了大约50%,选择性大约提高了3%,同时S i粉的最大转化率也有很大提高。     

二甲基二氯硅烷水解反应器研究进展

基于对甲基氯硅烷单体生产中水解反应特点的分析,论述了国内外几种水解反应器的结构特点,着重介绍了几种水解反应器在工业应用过程中存在的优缺点,并对水解反应器未来的发展方向进行了展望。     

有机硅高沸物催化裂解制单硅烷催化剂研究进展

介绍了近年来通过高温裂解法、催化裂解法将有机硅高沸物转化成单硅烷的研究进展,重点评述了催化裂解高沸物的氯化铝及其复合含盐催化剂、有机胺及其盐催化剂、过渡金属及其化合物催化剂、分子筛和活性炭催化剂。     

甲基二氯硅烷-二甲基二氯硅烷-苯体系等压汽液平衡

卤代硅烷的相平衡数据为硅烷生产所需,而这方面的研究又较缺乏,尤其是甲基乙烯基二氯硅烷生产中所需的汽液相平衡数据尚未见报道.本文用新型泵式沸点仪测定了常压（101.325 kPa ）下甲基二氯硅烷＋二甲基二氯硅烷＋苯三元体系和三个二元体系在不同液相组成时的泡点.由所测的二元系数据,用过量自由焓Q函数间接法推算了与之平衡的汽相组成,获得的汽液相平衡数据（VLE）符合热力学一致性;用最小二乘法求出二元体系的Wilson、NRTL、Margules、van Laar方程最佳配偶液相活度系数模型参数,所得的最佳配偶液相活度系数模型参数较好地满足于系统;将所得的最佳Wilson模型参数直接用于该体系三元系汽液相平衡数据的预测,将计算的泡点与实验测得的泡点作了比较,其拟合精度良好,关联结果令人满意;给出了苯溶液中甲基二氯硅烷对二甲基二氯硅烷的相对分离因子.硅烷二元系、多元系的热力学模型及VLE数据可为该体系的分离设计提供必要的理论依据.     

固载AlCl_3催化甲基三氯硅烷/三甲基氯硅烷再分配反应实验研究

针对有机硅单体二甲基二氯硅烷生产中的副产物—甲基三氯硅烷(—甲)和三甲基氯硅烷(三甲),采用固载 AlCl_3催化剂,在800mm×20mm(内径)的固定床反应器中进行一甲和三甲的再分配反应,制得二甲基二氯硅烷。通过催化剂筛选试验,结果表明以活性炭为载体的固载 AlCl_3催化剂为佳。通过工艺条件实验,确定了在活性炭固载 AlCl_3催化剂上一甲和三甲再分配反应的适宜工艺条件为:反应物摩尔比为1.0.液时空速 LHSV 为0.66 mL/(h·g-cat),反应温度为320℃,得到二甲收率70%左右。该催化剂还表现出一定的催化稳定性。     

A study of colored siloxane-based polyurethane ionomer

The reaction of dye with toluene diisocyanate and dimethyldichlorosilane in the presence of other additives to form a colored siloxane-based polyurethane (PU) ionomer has been proven to occur by infrared spectra. In aqueous solution, the number-average particle size for the colored siloxane-based PU ionomer was found to increase with an increase in the NCO-to-OH ratio, dye concentration, and dimethyldichlorosilane concentration, as a result of increased free volume of the ionomer molecules. It is worthy to note that the amount of air diffusing into the film cast from colored siloxane-based PU ionomer was found to increase with an increase in the concentration of dimethyldichlorosilane instead of raising the ratio of NCO to OH or the concentration of dye, as a result of the formation of more porosities. In addition, the tensile strength of this film will be strengthened by raising the NCO/OH ratio or the concentration of dimethyldichlorosilane, whereas the elongation, on the other hand, can be substantially increased with increasing the concentration of dye instead of increasing the concentration of dimethyldichlorosilane for use in the PU ionomer system. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2097–2105, 1998     

影响二甲基二氯硅烷选择性的原因分析

分析了影响二甲基二氯硅烷(简称二甲)选择性的几个因素(包括硅粉的质量、催化剂及触体、进料装置)。通过固定硅粉的来源、添加Cu-P催化剂、在进料装置加装干燥设备等改进措施,使二甲的选择性由64.8%提高到87.4%。     

Synthesis of silane-modified polyphosphate esters and its application in transparent flame-retardant coatings

Polyphosphate ester (PPAE) made from poly(phosphoric acid), pentaerythritol, and 1,3-butylene glycol has been synthesized. The PPAE reacted with dimethyldichlorosilane (DMDCS) to improve its thermal stability and flame retardancy. Four silane-modified polyphosphate esters (SiPPAEs) were obtained. FTIR, ³¹P NMR, and ²⁹Si NMR results showed that the Si Cl bond of DMDCS could react with the C OH and P OH bonds of PPAE, producing Si O C and P O Si bond in SiPPAEs. Different transparent coatings were obtained by mixing the PPAE and SiPPAEs with amino resin. The results of TGA showed that the stability of SiPPAEs was higher than that of PPAE. With the increase of silane content, the thermal stability of the coating increased. As the silane content increased within a certain range, the fire resistance and expansion coefficient increased. But too high silane content had adverse effects on the expansion and reduced the overall insulation effect. The digital photos and SEM/EDX microphotographs of coatings after combustion showed that silica segments could enriched in the surface to form a hard protective layer to prevent further degradation of the char layer. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47199.     

有机硅高沸物裂解歧化制备二甲基二氯硅烷的研究进展

在直接法合成甲基氯硅烷单体过程中，除目标产物二甲基二氯硅烷外，还产生了大量的高沸物。本文介绍了催化裂解歧化有机硅高沸物制备二甲基二氯硅烷的研究进展。