N-甲基吗啉的合成研究

以亚磷酸二氢钠、多聚甲醛和吗啉为原料合成了 N-甲基吗啉 ,探讨了反应温度、原料配比、反应时间对收率的影响 ,得出了最佳反应条件 :反应温度为 1 1 5℃ ,反应时间为 2 0 min,原料配比为 n(C4 H9NO)∶ n(HCHO) n∶ n(Na H2 PO3) =1∶ 1 .2∶ 0 .5 6。产物收率可达 95 % ,纯度为 98%。     

氮-磷-氯型皮革阻燃复鞣剂的合成及应用

选取亚磷酸二甲酯与丙烯酰胺在甲醇钠的催化作用下反应,制得中间体3-二甲氧磷酰基丙酰胺,后再利用中间体与环氧氯丙烷反应,合成出具有复鞣性能的氮-磷-氯皮革阻燃复鞣剂。讨论了反应物配比、反应温度、反应时间等条件对聚合反应的影响,确定了最佳反应条件:中间体与环氧氯丙烷的摩尔比为1.0:1.5,反应温度为100℃,反应时间为6h。将该合成的阻燃复鞣剂施加于皮革复鞣工段,利用阻燃检测法测试皮革的阻燃性能,试验发现,所得皮革制品的氧指数、有焰燃烧时间、无焰燃烧时间、烟密度、燃烧速率,均比未施加阻燃复鞣剂有显著提高,且所得制品在感官指标和力学方面,均比未施加阻燃复鞣剂的皮革有显著提高。     

抗氧剂168的合成工艺研究

研究了酯化法合成抗氧剂168[亚磷酸三（2,4二叔丁基苯基）亚磷酸酯]的工艺条件。以68．8g（1／3mol）2,4-二叔丁基苯酚和15．4g（1／9mol）三氯化磷为原料,催化剂三乙胺,反应温度140—150℃、反应时间2．5h的条件下进行酯化反应,经异丙醇结晶后得三（2,4-二叔丁基苯基）亚磷酸酯。平均收率95％。     

Exfoliated Layered Manganese Trichalcogenide Phosphite (MnPX3, X = S,Se) as Electrocatalytic van der Waals Materials for Hydrogen Evolution

Layered metal trichalcogen phosphites, also entitled as metal phosphorus chalcogenides (MPX₃), have regained abundant interest, not only due to their magnetic properties, but also due to promising performances in energy storage and conversion. Herein, two different layered manganese trichalcogen phosphites, MnPX₃ (X = S, Se), are synthetized and submitted to shear force exfoliation. Structural and morphological characterization point to the fact that exfoliated MPX₃ (exf‐MnPX₃) undergo mainly a downsizing process, alongside with delamination. Layered exf‐MnPSe₃ has the lowest onset potential for hydrogen evolution reaction (HER) in both media. In acidic media, a comparative improvement of 350 mV is observed for exf‐MnPSe₃ relative to the bulk MnPSe₃. The materials stability as electrocatalysts is also tested for HER in a wide pH range, in which exf‐MnPSe₃ has a good stability after 100 cycles. The improved performance of exf‐MnPSe₃ can be correlated with the lower relative abundance of Mn and P oxides detected in the Mn 2p and P 2p core levels. Such materials show a great promise for future in a hydrogen‐based economy.     

Cobalt‐Doped Nickel Phosphite for High Performance of Electrochemical Energy Storage

Compared to single metallic Ni or Co phosphides, bimetallic Ni–Co phosphides own ameliorative properties, such as high electrical conductivity, remarkable rate capability, upper specific capacity, and excellent cycle performance. Here, a simple one‐step solvothermal process is proposed for the synthesis of bouquet‐like cobalt‐doped nickel phosphite (Ni₁₁(HPO₃)₈(OH)₆), and the effect of the structure on the pseudocapacitive performance is investigated via a series of electrochemical measurements. It is found that when the cobalt content is low, the glycol/deionized water ratio is 1, and the reaction is under 200 °C for 20 h, the morphology of the sample is uniform and has the highest specific surface area. The cobalt‐doped Ni₁₁(HPO₃)₈(OH)₆ electrode presents a maximum specific capacitance of 714.8 F g^?1. More significantly, aqueous and solid‐state flexible electrochemical energy storage devices are successfully assembled. The aqueous device shows a high energy density of 15.48 mWh cm^?2 at the power density of 0.6 KW cm^?2. The solid‐state device shows a high energy density of 14.72 mWh cm^?2 at the power density of 0.6 KW cm^?2. These excellent performances confirm that the cobalt‐doped Ni₁₁(HPO₃)₈(OH)₆ are promising materials for applications in electrochemical energy storage devices.     

无酚法新工艺合成双十六烷基季戊四醇二亚磷酸酯

以季戊四醇、亚磷酸三乙酯和十六醇为原料，合成了双十六烷基季戊四醇二亚磷酸酯。考察了反应温度、反应时闻、催化荆及物料配比对产品收率的影响。实验结果表明，整个工艺过程可分为两步，合成季戊四醇二亚磷酸酯中间体时，最佳的工艺条件为：亚磷酸三乙酯、季戊四醇的摩尔比为2．05：1，催化剂的用量为季戊四醇质量的3％，反应温度为130℃，时间为2．5h；在合成双十六烷基季戊四醇二亚磷酸酯时，十六醇与中间体季戊四醇二亚磷酸酯的摩尔比为2．05：1，反应温度为160℃，时间2．5h。合成的产品中无酚无三废产生，产品元素分析及红外光谱与目的产物相一致。     

多功能阻燃剂聚醚多元醇膦酸酯/亚磷酸酯的合成

以丙三醇作为起始剂,三溴苯酚缩水甘油醚、环氧氯丙烷及环氧丙烷为共聚单体,以三氟化硼/四氢呋喃为催化剂合成的阻燃聚醚多元醇作原料,与亚磷酸三甲酯进行酯交换反应和Arbuzov重排反应,合成了新型聚醚多元醇膦酸酯/亚磷酸酯(PEPP)。通过元素分析和IR及1HNMR等分析方法对其化学结构进行了表征。考察了反应物料比对多元醇(HIROL-II)的性能和PEPP应用性能的影响。试验结果表明,适宜的环氧丙烷/环氧氯丙烷/三溴苯酚缩水甘油醚物质的量比是6∶1 1∶1,用23%PEPP制备的聚氨酯泡沫氧指数为31。PEPP是一种热稳定性高、阻燃效果好,同时兼有增塑剂和抗氧剂功能的新型橡塑助剂。     

国产和进口亚磷酸酯抗氧剂的对比和评价

为了考察辅助抗氧剂168(亚磷酸酯类)的应用性能,对几种进日、国产抗氧剂168进行了对比和评价研究,重点对抗氧剂168在树脂后加工中的性能进行系统的考察。     

亚磷酸酯类配体对镍系顺丁橡胶催化体系的影响

研究了在Ni(naph) 2 -Al(i -Bu) 3 -BF3 ·OEt2 (简称Ni -Al-B)体系中添加亚磷酸酯类配体(P)对丁二烯聚合反应的影响 ,用GPC ,FTIR表征了聚合物结构。结果表明 ,当Al/B(摩尔比 )为 0 .3～ 0 .7,P/Ni(摩尔比 )不大于 0 .5时 ,体系具有较高的转化率 ;当P/Ni增大时 ,聚合物的特性黏数明显降低。该反应是快引发、稳态逐步增长、无终止的聚合反应。聚合物的重均相对分子质量可通过改变P/Ni或Al/B进行调节。随P/Ni增大 ,聚合物的顺 - 1,4结构摩尔分数降低 ,反 - 1,4结构摩尔分数升高