石油学报(石油加工)
石油學報(石油加工)
석유학보(석유가공)
ACTA PETROLEI SINICA(PETROLEUM PROCESSING SECTION)
2009年
6期
819-825
,共7页
硫代磷酰胺酯%润滑性%取代基%Hammett常数%电负性%作用机理
硫代燐酰胺酯%潤滑性%取代基%Hammett常數%電負性%作用機理
류대린선알지%윤활성%취대기%Hammett상수%전부성%작용궤리
thiophosphoric amide%lubricity%substituents%Hammett constant%electronegativity%action mechanism
采用四球机和SRV试验机研究了3类不同结构的硫代磷酰胺酯(TPA)的抗磨有效性,包括硫代磷酰单胺酯(TPMA)、硫代磷酰双胺酯(TPDA)和二硫代磷酰单胺酯(DPMA).结果表明,TPA通常有较好的抗磨性和承载能力.其润滑性取决于酯基和胺基的结构、取代基的电负性和摩擦条件.在单向滑动和往复运动中性能都较佳的是硫脲基上连接有强烈吸电子作用的取代基的O-乙基、N-烷基和硫脲基单硫代磷酰胺酯(EAPTUT).某些TPA的性能优于ZDTP、MoDTP、硫代磷酸酯、膦酸次膦酸胺盐、T_(305)和T_(307)等商品化的抗磨剂.1个TPA分子中同时含有S、P、N基团,分子内相互牵制作用使每个功能团都不会过度活泼,摩擦过程中的腐蚀磨损和磨粒磨损很易平衡,总磨损最小.SRV试验中每次往复运动磨出新鲜金属表面仅费时百分之几秒,而活性不够的抗磨剂可能无法及时生成新表面保护膜.
採用四毬機和SRV試驗機研究瞭3類不同結構的硫代燐酰胺酯(TPA)的抗磨有效性,包括硫代燐酰單胺酯(TPMA)、硫代燐酰雙胺酯(TPDA)和二硫代燐酰單胺酯(DPMA).結果錶明,TPA通常有較好的抗磨性和承載能力.其潤滑性取決于酯基和胺基的結構、取代基的電負性和摩抆條件.在單嚮滑動和往複運動中性能都較佳的是硫脲基上連接有彊烈吸電子作用的取代基的O-乙基、N-烷基和硫脲基單硫代燐酰胺酯(EAPTUT).某些TPA的性能優于ZDTP、MoDTP、硫代燐痠酯、膦痠次膦痠胺鹽、T_(305)和T_(307)等商品化的抗磨劑.1箇TPA分子中同時含有S、P、N基糰,分子內相互牽製作用使每箇功能糰都不會過度活潑,摩抆過程中的腐蝕磨損和磨粒磨損很易平衡,總磨損最小.SRV試驗中每次往複運動磨齣新鮮金屬錶麵僅費時百分之幾秒,而活性不夠的抗磨劑可能無法及時生成新錶麵保護膜.
채용사구궤화SRV시험궤연구료3류불동결구적류대린선알지(TPA)적항마유효성,포괄류대린선단알지(TPMA)、류대린선쌍알지(TPDA)화이류대린선단알지(DPMA).결과표명,TPA통상유교호적항마성화승재능력.기윤활성취결우지기화알기적결구、취대기적전부성화마찰조건.재단향활동화왕복운동중성능도교가적시류뇨기상련접유강렬흡전자작용적취대기적O-을기、N-완기화류뇨기단류대린선알지(EAPTUT).모사TPA적성능우우ZDTP、MoDTP、류대린산지、련산차련산알염、T_(305)화T_(307)등상품화적항마제.1개TPA분자중동시함유S、P、N기단,분자내상호견제작용사매개공능단도불회과도활발,마찰과정중적부식마손화마립마손흔역평형,총마손최소.SRV시험중매차왕복운동마출신선금속표면부비시백분지궤초,이활성불구적항마제가능무법급시생성신표면보호막.
Three types of thiophosphoric amides (TP A), I.e.thiophosphoric monoamide(TPMA), thiophosphoric diamide(TPDA), and dithiophosphoric monoamide(DPMA) had been tested on a Four Ball machine and a SRV tester for their relative antiwear effectiveness.The results indicated that three types of TPA, in general, had fairly good load carrying capacity and antiwear performance.The lubricity of these compounds was found to be dependent upon the structure of both the ester groups and the amine groups, the electronegativity of substituents, as well as rubbing conditions.The best performance in both unidirectional sliding and reciprocating sliding was observed for those O-ethyl N-alkyl phosphoro (thioureido) thioates (EAPTUT) in which a strong electron-withdrawing substituent was linking to the thioureido group.The superiority of some substituted EAPTUT and dialkyl dithiophosphoramidates (DADTPA) to many commercially available antiwear additives, including ZDDP, MoDTP, thiophosphates, amine salt of phosphonic acids and phosphinic acids, T_(305) and T_(307), was probably related to the intramolecular synergism of substituents, the effect of electron-withdrawing substituent on the cleavage of the P-N bond, as well as the high soften point of SPN type polymer films formed in rubbing surface.Functional groups containing sulphur, phosphorus and nitrogen on a single TPA molecule could control the molecule interaction with the surface without making any one bond too active, thus balance adhesive wear and corrosive wear and result in minimum total wear.In SRV test a fresh metal surface was generated after every cycle, which spent only a few hundredths seconds and could not allow low activity additives to form a protective surface film in time.