To overcome the limitations of traditional experimental“trial and error”methods in lubricant additive design,a new molecular design method based on molecular structure parameters is established here.The molecular me...To overcome the limitations of traditional experimental“trial and error”methods in lubricant additive design,a new molecular design method based on molecular structure parameters is established here.The molecular mechanism of the antioxidant reaction of hindered phenol,diphenylamine,and alkyl sulfide are studied via molecular simulations.Calculation results show that the strong electron-donating ability and high hydrogen-donating activity of the antioxidant molecule and the low hydrogen-abstracting activity of free radicals formed after dehydrogenation are the internal molecular causes of the shielding of phenol and diphenylamine from scavenging peroxy free radicals,and the strong electron-donating ability is the internal molecular cause of the high activity of thioether in decomposing alkyl hydrogen peroxide.Based on this antioxidant molecular mechanism,a molecular design rule of antioxidant is proposed,namely“high EHOMO,large Q(S),low bond dissociation energy BDE(O—H)and BDE(N—H)”.Two new antioxidants,PAS-I and PAS-II,are designed and prepared by chemical bonding of hindered phenol,diphenylamine,and sulfur atoms.Experimental results show that these antioxidants both have excellent antioxidant effects in lubricating oil,and that PAS-II is the superior antioxidant,consistent with theoretical predictions.展开更多
In this paper,an ab initio,local density functional(LDF)method was used to explore the relationship between the molecular properties of additives and the lubricating performance of aluminum rolling oil.The structural ...In this paper,an ab initio,local density functional(LDF)method was used to explore the relationship between the molecular properties of additives and the lubricating performance of aluminum rolling oil.The structural properties of butyl stearate,dodecanol,docosanol,and methyl dodecanoate were studied according to the density functional theory.The calculated data showed that the atoms in or around the functional groups might be likely the reacting sites.Because of the different functional groups and structure of ester and alcohol,two types of complex additives,dodecanol and butyl stearate,methyl dodecanoate and butyl stearate,respectively,were chosen for studying their tribological properties and performing aluminum cold rolling experiments.The test results agreed with the calculated results very well.The complex ester,viz.methyl dodecanoate and butyl stearate,had the best lubricating performance with a friction coefficient of 0.084 1 and a permissive-rolling thickness of 0.040 mm as compared with that of dodecanol-butyl stearate-base oil formulation.展开更多
In this paper, the propene oligomerization reaction catalyzed by phosphotungstic acid supported on two kinds of silica gel was studied, it had been found out that the conversion of propene catalyzed by the type A sili...In this paper, the propene oligomerization reaction catalyzed by phosphotungstic acid supported on two kinds of silica gel was studied, it had been found out that the conversion of propene catalyzed by the type A silica gel-phosphotung- stic acid catalyst was 3.38 m%, while the conversion of propene catalyzed by the type B silica gel-phosphotungstic acid catalyst was 90.1 m% with a nonene selectivity of 42.33 m%, and a dodecene selectivity of 31.79 m%. The influence of reaction temperature, pressure and liquid hourly space velocity （LHSV） on the reaction catalyzed by the type B silica gel- phosphotungstic acid catalyst was investigated. It had been verified that when the reaction temperature increased from 170 ~C to 190 ~C, the conversion of propene increased while the selectivity of nonene and dodecene decreased; when the re- action pressure increased from 3.5 MPa to 4.5 MPa, the conversion of propene increased also, and the selectivity of nonene and dodecene changed very little. The conversion of propene at a space velocity of between 0.5 h-1 and 1.0 h-~ was higher than that achieved at 2.0 h-~, but the selectivity of nonene and dodecene did not show regular fluctuations. An optimum conversion of propene （91.05 m%） and an optimum selectivity of nonene and dodecene （89.51 m%） could be achieved at a reaction temperature of 170 ~C, a reaction pressure of 4.5MPa, and a LHSV of 1.0 fit. The experiments on catalyst life showed that the activity of the type B silica gel-phosphotungstic acid catalyst could be only maintained in 25 hours, and the reason was explained also.展开更多
In this paper, four kinds of polymethacrylates(PMAs) used as multifunctional additives were synthesized from quaternary C1—C14 methacrylate, among which sample 4 exhibited relatively better performance. According to ...In this paper, four kinds of polymethacrylates(PMAs) used as multifunctional additives were synthesized from quaternary C1—C14 methacrylate, among which sample 4 exhibited relatively better performance. According to the methacrylate ratio of sample 4, the optimized reaction conditions of PMA were explored by orthogonal experiments comprising 4 factors and 3 levels, and the optimized reaction conditions covered an initiator dosage of 0.8 %, a molecular weight regulator dosage of 0.4%, a reaction temperature of 95 ℃ and a reaction time of 8.5 h. When the optimized PMA samples were used to formulate the 75W/90 automotive gear base oil, they exhibited improved shear stability and good low temperature property. In comparison with foreign commercial polymethacrylate GP, the optimized PMA samples exhibited better thickening ability, similar shear stability and slightly weak low temperature property, with their performance being the same as GP's on the whole. The slight difference in the performance between the optimized PMA and GP was attributed to the difference of chain length of copolymers and the distribution of relative molecular mass between them.展开更多
The conditions for synthesis of overbased lithium sulfonate were investigated in this paper.Various performances of lithium sulfonate,such as its corrosiveness,high temperature detergency,oxidization stability,wear re...The conditions for synthesis of overbased lithium sulfonate were investigated in this paper.Various performances of lithium sulfonate,such as its corrosiveness,high temperature detergency,oxidization stability,wear resistance,dispersity, bubble ability and acid neutralization capability were evaluated in a 15W/40 thickened oil.On companson with other sulfonates, the overbased lithium sulfonate exhibited a lowest sulphate ash,a best detergency and a moderate corrosiveness in 15w/40CD and 15w/40SD oil formulations.However,the weak wear resistance was its only disadvantage.展开更多
文摘To overcome the limitations of traditional experimental“trial and error”methods in lubricant additive design,a new molecular design method based on molecular structure parameters is established here.The molecular mechanism of the antioxidant reaction of hindered phenol,diphenylamine,and alkyl sulfide are studied via molecular simulations.Calculation results show that the strong electron-donating ability and high hydrogen-donating activity of the antioxidant molecule and the low hydrogen-abstracting activity of free radicals formed after dehydrogenation are the internal molecular causes of the shielding of phenol and diphenylamine from scavenging peroxy free radicals,and the strong electron-donating ability is the internal molecular cause of the high activity of thioether in decomposing alkyl hydrogen peroxide.Based on this antioxidant molecular mechanism,a molecular design rule of antioxidant is proposed,namely“high EHOMO,large Q(S),low bond dissociation energy BDE(O—H)and BDE(N—H)”.Two new antioxidants,PAS-I and PAS-II,are designed and prepared by chemical bonding of hindered phenol,diphenylamine,and sulfur atoms.Experimental results show that these antioxidants both have excellent antioxidant effects in lubricating oil,and that PAS-II is the superior antioxidant,consistent with theoretical predictions.
基金the financial support of this study provided by the National Natural Science Foundation of China(No.51274037)the Cooperation Program between USTB and SINOPEC(No.112116)
文摘In this paper,an ab initio,local density functional(LDF)method was used to explore the relationship between the molecular properties of additives and the lubricating performance of aluminum rolling oil.The structural properties of butyl stearate,dodecanol,docosanol,and methyl dodecanoate were studied according to the density functional theory.The calculated data showed that the atoms in or around the functional groups might be likely the reacting sites.Because of the different functional groups and structure of ester and alcohol,two types of complex additives,dodecanol and butyl stearate,methyl dodecanoate and butyl stearate,respectively,were chosen for studying their tribological properties and performing aluminum cold rolling experiments.The test results agreed with the calculated results very well.The complex ester,viz.methyl dodecanoate and butyl stearate,had the best lubricating performance with a friction coefficient of 0.084 1 and a permissive-rolling thickness of 0.040 mm as compared with that of dodecanol-butyl stearate-base oil formulation.
文摘In this paper, the propene oligomerization reaction catalyzed by phosphotungstic acid supported on two kinds of silica gel was studied, it had been found out that the conversion of propene catalyzed by the type A silica gel-phosphotung- stic acid catalyst was 3.38 m%, while the conversion of propene catalyzed by the type B silica gel-phosphotungstic acid catalyst was 90.1 m% with a nonene selectivity of 42.33 m%, and a dodecene selectivity of 31.79 m%. The influence of reaction temperature, pressure and liquid hourly space velocity （LHSV） on the reaction catalyzed by the type B silica gel- phosphotungstic acid catalyst was investigated. It had been verified that when the reaction temperature increased from 170 ~C to 190 ~C, the conversion of propene increased while the selectivity of nonene and dodecene decreased; when the re- action pressure increased from 3.5 MPa to 4.5 MPa, the conversion of propene increased also, and the selectivity of nonene and dodecene changed very little. The conversion of propene at a space velocity of between 0.5 h-1 and 1.0 h-~ was higher than that achieved at 2.0 h-~, but the selectivity of nonene and dodecene did not show regular fluctuations. An optimum conversion of propene （91.05 m%） and an optimum selectivity of nonene and dodecene （89.51 m%） could be achieved at a reaction temperature of 170 ~C, a reaction pressure of 4.5MPa, and a LHSV of 1.0 fit. The experiments on catalyst life showed that the activity of the type B silica gel-phosphotungstic acid catalyst could be only maintained in 25 hours, and the reason was explained also.
文摘In this paper, four kinds of polymethacrylates(PMAs) used as multifunctional additives were synthesized from quaternary C1—C14 methacrylate, among which sample 4 exhibited relatively better performance. According to the methacrylate ratio of sample 4, the optimized reaction conditions of PMA were explored by orthogonal experiments comprising 4 factors and 3 levels, and the optimized reaction conditions covered an initiator dosage of 0.8 %, a molecular weight regulator dosage of 0.4%, a reaction temperature of 95 ℃ and a reaction time of 8.5 h. When the optimized PMA samples were used to formulate the 75W/90 automotive gear base oil, they exhibited improved shear stability and good low temperature property. In comparison with foreign commercial polymethacrylate GP, the optimized PMA samples exhibited better thickening ability, similar shear stability and slightly weak low temperature property, with their performance being the same as GP's on the whole. The slight difference in the performance between the optimized PMA and GP was attributed to the difference of chain length of copolymers and the distribution of relative molecular mass between them.
文摘The conditions for synthesis of overbased lithium sulfonate were investigated in this paper.Various performances of lithium sulfonate,such as its corrosiveness,high temperature detergency,oxidization stability,wear resistance,dispersity, bubble ability and acid neutralization capability were evaluated in a 15W/40 thickened oil.On companson with other sulfonates, the overbased lithium sulfonate exhibited a lowest sulphate ash,a best detergency and a moderate corrosiveness in 15w/40CD and 15w/40SD oil formulations.However,the weak wear resistance was its only disadvantage.
