【作者】 胡志孟；

【导师】 黄黔； 党鸿辛；

【作者基本信息】 上海大学 ， 机械设计及理论， 1999， 博士

【摘要】 本文提出了两类润滑油添加剂，合成了无活性元素的羟基植物油脂肪酸和含活性元素硫的硫化植物油脂肪酸，其中羟基植物油脂肪酸是无污染的绿色润滑剂，对环境保护有重要意义。用红外光谱、元素分析、热重分析和毛细管熔点测定法对这两类添加剂进行了结构表征，研究了这两类添加剂在液体石蜡中的摩擦学特性，用X光电子能谱和反射红外光谱分析了它们的摩擦表面。基于上述结果，提出了这两类添加剂各自的润滑作用机理，从而指出用植物油作原料，可以合成得到绿色润滑剂，主要研究结果有： 1．氧元素在润滑机理中有着关键作用，无论在含活性元素的硫化植物油脂肪酸，还是在不含活性元素的纯碳、氢和氧的羟基植物油脂肪酸中，氧元素始终影响着添加剂的润滑性。 2．羟基植物油脂肪酸是一类潜在的抗磨极压剂。13，14-二羟基廿二酸的抗磨极压性与二烷基二硫代磷酸锌（ZDDP）相当，可取代ZDDP，由于它的合成过程没有污染，是一种绿色化学合成，且原材料取自清洁而丰富的植物油，故它是一种完全的绿色润滑剂。 3．羟基植物油脂肪酸的润滑作用机理是在摩擦表面分子间酯化反应生成了摩擦聚酯膜，由于这层膜的存在，减少了金属的摩擦和磨损。 4．基于生成酯的特征吸收峰V_c-o-c^as的波数位移，用红外光谱理论分析了羟基酸生成聚酯的立体构型和聚酯膜的强度。1999年上海大学博士学位论文用经典力学和量子力学模型分别导出轻基酸的抗磨性顺序规律与*票。一。振动吸收峰位置的内在联系，合理解释了，器。_。从小到大的顺序与经基酸的抗磨性从好到差的顺序的一致性，即13，14一二轻基廿二酸>l 3（l4）一经基廿二酸=9，10一二轻基十八酸>9，10，12一三轻基十八酸>9（10）一经基十八酸.13，14一二经基廿二酸形成了网状聚醋膜，9（10）一经基十八酸形成了线状聚醋膜，13（14）一经基廿二酸形成的聚醋膜由于碳链长度补偿了其膜的强度而使抗磨性与9，10一二经基十八酸相近.9，10，12一三经基十八酸由于轻基的位阻作用使一OH易离去而生成不饱和经基酸(酮醚，由于分子中不饱和键的存在，使其润滑性变差，故9，10，12-三经基十八酸的抗磨性没有9，10一二经基十八酸的抗磨性好. 5.拓展了冷法硫化工艺的应用.用低温硫化工艺和复分解反应制备得到了无臭硫化植物油脂肪酸. 6.经基植物油脂肪酸的抗磨性好于硫化植物油脂肪酸，但硫化植物油脂肪酸的极压性好于经基植物油脂肪酸.二轻基廿二酸的极压性与不含氧基团的硫化烯烃十分接近，以液体石蜡为基础油，最大无卡咬负荷尸B值，前者为539N，后者为588N，两者相差‘49N，可以看出，氧基团的作用是十分显著的，即无活性元素的二经基廿二酸的极压性可以十分接近于含活性元素的抗磨极压剂硫化烯烃. 7.硫化植物油脂肪酸的抗磨性规律:硫化十八酸>硫化廿二酸，即抗磨性长碳链的硫化植物油脂肪酸不如短碳链的硫化植物油脂肪酸，极压性顺序恰好相反.但硫化植物油脂肪酸的抗磨极压性均比不含氧基团的硫化烯烃要好，可见氧基团对含活性元素的添加剂的抗磨极压性的作用是很大的. 8.硫化植物油脂肪酸的润滑作用机理是它在摩擦时，首先 羚基和硫化植物油脂肪酸的摩擦学研究是活性元素硫S或生成的硫醇RSH吸附于金属表面，靠这层化学吸附膜起抗磨作用，含S量越高的硫化植物油脂肪酸抗磨性越好，故抗磨性顺序含S量高的硫化十八酸>含硫量低的硫化廿二酸;在极压区，靠添加剂分子链被打断，在金属表面形成硫化铁和氧化铁的混合润滑膜起极压作用.这层混合润滑膜比单一的FeS膜有效，经IR分析，由于硫化廿二酸的分子打断得比较彻底，因而其极压性就好. 经基和硫基团在植物油脂肪酸中的作用，经基可参与摩擦聚合物的形成，硫基团可参与牺牲性反应膜FeS的形成，氧基团和硫基团有协同作用，由于氧使硫化植物油脂肪酸的抗磨极压性大大好于不含氧的硫化烯烃.更多还原

【Abstract】 Two types of lubricating oil additives which are hydroxy vegetable oil fatty acids without active elementes and sulphurized fatty acids with active elements sulphur were developed in this thesis, in which, hydroxy vegetable oil fatty acids are "green" lubricants without contamination, so they have significance for environmental protection. Chemical structure characterization of these additives synthesized were carried out by infrared spectrometry, elementary analysis, thermogravimettic analysis and capillary melting poinp test, triobological characteristics of those additives in liguid paraffin were studied, and rubbing surfaces of oils containing these addtives were analyzed by X-ray Photoelectron Spectroscopy and Refection Micro Fourier Transform Infrared Spectroscopy, respectively. Base on these results, each lubrication mechanism of two types of additives were put forward, thus we point out that green lubricants may be synthesized using vegetable oils, main research results of this thesis are as follows:1. Oxygen plays critical roles in lubrication mechanism. Oxygen affects the lubrication mechanism of additives all along, whether in sulfurized vegetable oil fatty acids containing active element or not in hydroxy vegetable ,oil fatty acids with pure carbon, hydrogen and oxygen not containing active element.2. Hydroxy vegetable oil fatty acids are a kind of potential antiwear and extreme pressure（EP）agents. The antiwear and EP properties of 13,14-dihydroxydocosanoic acid are approched to Zinc dialkyldithiophosphates （ZDDP）, so it will replace ZDDP. Because preparation process is green chemical synthesis without contaminationand raw materials come from clean and rich vegetable oils, it is competely green lubricants.3. The lubrication mechanism of hydroxy vegetable oil fatty acids is that the friction polyester film is formed on rubbing surfaces by intermolecular esterification of hydroxy fatty acids, and friction and wear of metal pairs was decreased sharply during to the presence of this film.4. The strength and steroconfiguration of polyester film were analyzed by Infrared Spectroscopy theory based on the wave numberdisplacement of characteristic absorption peak vasc_0c of the ester formed. Internal relations between antiwear order law of hydroxy fatty acids and vibration absorption peak vf_0c of polyester formedby hydroxy fatty acids was deduced by quantum mechanics and classical mechanics,and the antiwear order of hydroxy fatty acids was reasonably explained, that is 13,14-dihydroxydocosanoic acid>13（14）-monohydroxydocosanoic acid=9,10-dihydroxyoctadecanoic acid >9,10,12-trihydroxyoctadecanoic acid > 9（10）-monohydroxyoctadecanoic acid. A net-like polyester film is formed by 13,14-dihydroxydocosanoic acid and a linear polyester film is formed by 9,（10）-monohydroxyoctadecanoic acid and 13（14）-monohydroxydocosanoic acid.5. The application of cold vulcanization technology was developed, non-odour sulphurized vegetable oil fatty acids were prepared by low temperature vulcanization and metathetical reaction.6. The antiwear properties of hydroxy vegetable oil fatty acids are better than that ot sulphurized vegetable oil fatty acids , whereas the extreme pressure property is reciprocal,EP property of dihydroxy-docosanoic acid is very near to that of sulfurized olefin（SO） without oxygen group, in liquid paraffin base stocks, maximum non scuffing load PB of the former is 539N, PB of the latter is 588N. It is seen thatoxygen group function of additives is very remarkably in tribological characteristics, that is EP property of dihydroxydocosanoic acid without active element is very near to that of SO with active element sulfur.7. The antiwear rule of sulphurized vegetable oil fatty acid is, sulphurized octadecanoic acid > sulphurized docosanoic acid, and EP rule is exactly reciprocal, whereas the antiwear and EP properties of sulphurized vegetable oil fatty acid are better than that of SO without oxygen group, it was found that oxygen group function is also very import更多还原