凝胶丁腈共聚弹性体增韧聚甲醛的加工流变行为及力学性能

研究了聚甲醛(POM)/凝胶丁腈共聚弹性体(GNBE)共混物的熔体流动指数(MFI)、高压毛细管流变行为和力学性能。结果表明,共混物MFI随GNBE用量的增加下降较大。聚酰胺(PA)对POM/GNBE共混体系的MFI影响较小,而热塑性酚醛树脂(PFR)的影响显著。当PFR的质量份为4时,POM共混物的MFI达最小值(0.053g/min),约为未加增容剂POM共混物MFI的1/6。随着剪切速率的提高,共混物剪切黏度迅速与POM接近。这种黏度变化行为说明共混物比GNBE对剪切速率更敏感,共混物的黏度受POM的影响较大。随着剪切速率的提高,POM与GNBE的黏度比迅速减小,并接近1,说明POM和GNBE在高剪切速率下共混时,GNBE的液滴能够在POM连续相中分散达到最小。含20份GNBE的POM共混物在高剪切速率下的熔体表观黏度与POM相当;在PFR质量份为6时,POM共混物的缺口冲击强度达到21.6kJ/m2,超过了GNBE质量份为40的POM共混物。当PFR质量份为4时,共混物的缺口冲击强度为对应的不加增容剂共混物的冲击强度的2倍多,扯断伸长率提高了55.4%。     

Effect of Fe/Zn ratio in composite catalyst for synthesizing polyoxymethylene dimethyl ethers

Polyoxymethylene dimethyl ethers (PODE_n) are extremely effective diesel additives to reduce soot formation during combustion. We introduce a series of Fe-Zn composite solid acid catalysts (SO₄²⁻/xFe₂O₃-yZnO), for the condensation reaction of methanol and paraformaldehyde (PF) with a cheap and feasible route to efficiently synthesize PODE_n. These catalysts were characterized by different characterization techniques, namely BET, XRD, SEM, EDS, FTIR, and NH₃-TPD and the results showed that Fe/Zn molar ratios strongly influenced the physicochemical characteristics of catalysts, thus affecting the methanol conversion and PODE_1-6 and PODE_3-6 selectivity. Accordingly, the methanol conversion was decreased and the selectivity of PODE_3-6 was increased after increasing the Zn molar content. Comparatively, SO₄²⁻/Fe₂O₃-2ZnO exhibited superior catalytic activity among the various investigated catalysts due to the high acid density of strong acid sites. The optimal reaction conditions were observed to be at a 3.0 wt% catalyst loading (catalyst/reactant mass ratio), 2.5 hours ours of reaction time, a reaction temperature of 403 K, and a molar ratio of 3:1 of CH₂O to methanol, achieving a high selectivity of 99.09% PODE_1-6 and 28.23% PODE_3-6 with 55.16% methanol conversion during the reaction.     

高分子甲醛吸收剂对聚甲醛的热稳定性能与结构的影响

采用差示扫描量热仪（DSC）、热重分析仪（TGA）及偏光显微镜（PLM）研究高分子甲醛吸收剂共聚酰胺（COPA）和密胺树脂（MF）对聚甲醛（POM）的热稳定性能与结构的影响。结果表明：两种高分子甲醛吸收剂都能起到结晶成核剂的作用。同时COPA对POM的热稳定性效果优于ME的,但会提高POM的黄色指数,而MF会降低POM的黄色指数。     

甲醛回收塔防腐蚀技术探讨

针对在共聚甲醛生产过程中三聚甲醛合成工段甲醛回收塔甲酸腐蚀的问题,通过对近年来国内外常用缓蚀剂调查研究及机理分析,提出在甲醛回收塔非入料槽添加中和缓蚀剂的方法缓解设备腐蚀问题。通过对神华宁夏煤业集团公司6万吨聚甲醛项目生产实际情况的分析,论证了选择水溶性有机胺复配咪唑啉衍生物作为甲醛回收塔的中和缓蚀剂的可行性。     

润滑和载荷状态对聚甲醛齿轮服役性能的影响

基于齿轮耐久性能试验台开展了一系列干接触/油润滑下POM(聚甲醛)-POM齿轮副承载能力试验,并测量了服役过程中的轮齿温度、磨损量、齿廓精度和齿面形貌。试验发现,POM齿轮失效形式与载荷和润滑方式有关。通过对齿面微观形貌和磨屑表征,确认干接触下POM齿轮主要磨损模式为黏着磨损与磨粒磨损,而油润滑下POM齿轮失效形式为接触疲劳失效。由于润滑油减少了齿面摩擦,降低了运行温度,延缓了齿面劣化程度,因此POM齿轮在油润滑下的承载能力明显提高。     

聚甲醛多元耐磨复合材料的摩擦学特性

利用环块磨损试验机对模压法制备的Ekonol/G/MoS2/POM复合材料的摩擦学性能进行了测试,利用DSC、红外光谱（FTIR）分析方法对其磨屑进行了研究,用SEM方法对复合材料的磨损表面进行了观察和分析,进而对复合材料的磨损机理进行了探讨.结果表明：POM复合材料磨屑的熔点比相应模压材料有所降低,且磨屑的熔限比相应的模压材料有所加宽;随着Ekonol含量的增加,复合材料的摩擦因数和磨损量呈先减小后增大的趋势,其磨损机理发生了由犁沟、粘着磨损向疲劳磨损、磨粒磨损的转变。     

聚甲氧基二甲醚掺混比对柴油机性能及柴油机氧化催化器+催化型柴油机颗粒捕集器后处理系统的影响

以加装了柴油氧化型催化器(DOC)+催化型颗粒捕集器(CDPF)后处理系统的D30型高压共轨柴油机为研究机型,将聚甲氧基二甲醚(PODE)以0％、10％、30％三种体积比掺入柴油(分别记为P0、P10、P30)进行发动机台架试验,研究PODE掺混比对柴油机性能和后处理系统的影响.研究表明:负荷工况下,PODE掺混比越大...     

聚甲醛等温热降解

通过等温热失重(TG)和残留物红外光谱(FTIR)研究了聚甲醛(POM)在空气条件下的热氧降解动力学及机理,讨论了温度对聚甲醛初始降解速率以及热老化寿命的影响。结果表明,POM热氧降解的初始阶段符合一级反应动力学规律,POM在240℃下的降解速率常数比180℃高出100倍,其在230℃下的热老化寿命小于3min。POM在热氧降解过程中的FTIR分析表明,在1735cm-1处出现了典型的羰基吸收峰,标志着有氧存在下POM的降解遵循自由基引发断链的机理。     

Investigation of the Thermal Decomposition Properties of Polyoxymethylene

By testing the melt index （MI）, tensile strength and breaking extension ratio, the thermal ageing rate of polyoxymethylene （POM） was analyzed and compared. The surface morphology and type of function group of POM surface were observed and analyzed by SEM and XPS. The results show that the MI value increases gradually with the ageing time at 120℃, indicating that the thermal oxidation decomposition occurrs slowly. The effect of 20-day thermal ageing on the tensile strength and breaking extension ratio of POM is not obvious, showing that the ageing of POM is quite a long process. After 105-day, thermal ageing cracking and powdering occurr on the POM surface. XPS determination shows the Cls spectra of samples before and after ageing include two peaks of C-C and C-O, while after ageing the content of C-C decreases and the content of C-O increases, indicating that the thermal ageing of POM is mainly the breaking and decomposing of C-C bond. The Ols/Cls ratio of original samples is 56.98% and after 105-day thermal ageing the ratio is 72.92%.     

无标样聚甲氧基二甲醚校正因子的测定

聚甲氧基二甲醚是一种理想的新型柴油添加剂。针对聚甲氧基二甲醚组分缺少标样的问题,研究采用气相色谱技术,依据质量守恒原理测定并计算了不同聚合度聚甲氧基二甲醚组分的质量校正因子,以实现各组分含量的准确定量分析。根据反应过程的CH2O守恒及混合过程的质量守恒,对质量校正因子的准确性进行了验证,应用该校正因子计算所得到的质量相对误差小于4%。用此方法测定的校正因子准确度高于有效碳数估算法所得校正因子。该测定方法操作简单,可满足企业生产及实验室研究中聚甲氧基二甲醚产物的定量分析要求。