润滑科技信息平台

Lubricating oil additives

专利摘要

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基本信息

专利类型:
发明专利
申请/专利号:
US3595792DA
申请日期:
1968-04-04
专利申请人:
卡斯特罗尔有限公司
分类号:
["C07F9/00","C07F9/02","C10M137/10","C10M137/00","C10N10/04","C10N10/10","C10N30/06","C10N30/12","C10N40/08","C10M1/48"]
发明/设计人:
JOHN SCOTCHFORD ELLIOTT ， GERALD JOHN JOSEPH JAYNE ， ANTHONY DAVID BRAZIER
权利要求: 0. 009651. 772. 188. 638. 631:4Hed!0. 004140.910. 949. 499.381:10EXAMPLE 5Preparation of bismuth/zinc (1:1) salt of DTPA-2A mixture of dialkyl dithiophosphoric acids was prepared from isopropanol (199 g., 3.32 moles), capryl alcohol (600 g., 4.62 moles) and phosphorous pentasulphide (378 g. 1.7 moles) in the manner described in Example 1, but at a temperature of 80° C.Employing essentially the same method as described in Example 1 this dithiophosphoric acid (DTPA-2) (169 g. 0.5 moles) was added to a mineral oil slurry of bismuth and zinc oxides, the reaction being completed by the addition of further zinc oxide as described in Example 1. The weights of bismuth and zinc oxide employed were 13.97 g. (0.03 mole) and 14.52 g. (0.178 mole) respectively. The product had an acidity of 0.7 mg. KOH/g. and a pH of 5.3. It analysed as follows:Bi, 6.4% (calc. 6.2% )Zn. 4.9%> (calc. 6.4%) P, 7.44% (calc. 7.8%)EXAMPLE 6Preparation of bismuth/zinc (1:1) salt of di-(2-ethyl hexyl) dithiophosphoric acidEmploying essentially the same method as described in Example 1, di-2-ethylhexyl dithiophosphoric acid (111 g. 0.2 mole), prepared from 2-ethyl hexanol (1040 g. 8.0 moles) and phosphorus pentasulphide (444 g. 2.0 moles) at 80-90° C. was added to a mineral oil slurry of bismuth oxide and zinc oxide, the weights of bismuth and zinc oxides employed being 8.4 g. (0.018 mole) and 8.75 g. (0.107 mole) respectively.The product had an acidity of 0.93 mg. KOH/g. and a pH of 4.7. It analysed as follows:Bi, 4.3% (calc. 5.15%)Zn, 4.8% (calc. 4.95%)P, 6.75% (calc. 6.45%)EXAMPLE 7Preparation of bismuth/cadmium (1:1) salt of dimethyl hexyl) dithiophosphoric acidEmploying essentially the same method as described in Example 1, di-2-ethylhexyl dithiophosphoric acid (114.3 g.—0.3 mole), from a subsequent preparation similar to that in Example 6, was added to a mineral oil slurry of bismuth oxide and cadmium oxide, the weights of the bismuth and cadmium oxides being 11.6 g. (0.025 mole) and 11.3 g. (0.09 mole) respectively.The product had an acidity of 0.56 mg. KOG/g. and a pH of 4.4. It analysed as follows:Bi, 5.6% (calc. 6.6%) Cd, 7.3% (calc. 6.6%) P, 6.46% (calc. 6.1%)EXAMPLE 8Preparation of bismuth salt of DTPA-1This was prepared as described in Example 1 except that all the bismuth oxide (42.7 g. 0.0917 mole) was added at the beginning to the DTPA-1 (133 g. 0.5 mole). Twice the normal amount of mineral oil (48 g.) was required to maintain a clear solution. The additive had the following analysis:Bi, 15.0% (calc. 14.7%) P, 6.59% (calc. 6.64%)The additive was obtained by mixing 20% by weight of the above prepared bismuth salt with 80% by weight of a similarly prepared zinc salt of the same acid.In order to demonstrate the antioxidant properties of the additives of the present invention in a typical lubricating oil, blends were prepared in mineral oil A, which was a solvent refined mineral oil of viscosity approximately 160 seconds Redwood 1 at 140° F. These blends were all made up to contain 0.072% phosphorus and comparison was made with certain conventional zinc dialkyl dithiophosphates and with bismuth dialkyl dithiophosphates which did not contain zinc or cadmium. These oils were subjected to the well-known Rotary Bomb test, a description of which is given in British patent specification No. 1,023,380 on page 12 lines 5-22. The results of these tests and the conditions employed are given on Table IL The advantage of the additives of the present invention over the corresponding zinc or cadmium dithiophosphates is clearly seen from this table and in some cases the additives of the present invention also show an advantage over the simple bismuth salts.When the load carrying properties of the additives of the present invention are compared with those of the corresponding zinc dithiophosphates on the 4-ball machine at room temperature by the standard procedure employing a series of 1-minute runs at different loads, a distinct improvement in load carrying capacity is consistently obtained as judged by a comparison of the wear scar diameters at loads above the point of incipient seizure. In general it has been found that the higher the amount of bismuth dithiophosphate in the oil the smaller the wear scar diameter. When, however, wear tests are carried out on the 4-ball machine at low loads the amount of wear given by the bismuth dithiophosphates is significantly greater than that given by the corresponding zinc dithio-phosphates. The additives of the present invention, particularly the substantially neutral products obtained by the preferred method of preparation, often show a smaller increase in wear than would be anticipated from the amount of bismuth present. This is illustrated in Table III, which compares the results of tests carried out on blends of several dithiophosphates in mineral oil A, all these blends containing 0.056% phosphorus. The 4-ball machine was operated for periods of 1-hour under a 15 kg. load, the oil temperature being 50° C. It can be seen from Table III that additives of the present invention gave, under these conditions, wear scar diameters not greatly in excess of the corresponding zinc dithiophosphates, whereas the simple bismuth salts gave substantially increased wear.TABLE II-ROTARY BOMB TEST Temperature 150° C.3 metres of copper wireInitial pressure 90 p.s.l.Induction period Additive Percent (minutes)None_____________________________________________Zinc salt of DTPA-1-.......................... 0.75Bismuth salt of DTPA-1__________ 1.08Product of Example:1._________ 0.812 _________________________________ 0.803 _____________________________________ 0.784 ________________________________________ 0.77Zinc salt of DTPA-2_____________________________ 0.98Bismuth salt of DTPA-2__________________ 0.975Product of Example 5____________________________ 0.97Cadmium di (2-ethyl hexyl) dithiophosphate_____ 1.22Bismuth di (2-ethyl hexyl) di thiophosphate______ 1.17Product of Example 7____________________________ 1.11TABLE HL—4-BALL WEAR TESTS(15 kg.—1 hr — 50* C.)AdditivePercentMean wear scar diani.(mm.)Precent inc. in wear over line compoundZinc salt of DTPA-1______________. 0.580.296 .Bismuth salt of DTPA-1__________. 0.840.433Product of Example:1______________________________0.6250.3252______________________________. 0.620.286Nil3________________________________ 0.610.3134______________________________. 0.600.300Zinc di (2-ethyl hexyl) dithiophosphate............................._ 0.870.296 .Bismuth di (2-ethyl hexyl) dithiophosphate________________________ 0.9150. 400Product of Example 6............._ 0.830.312We claim:1. A lubricating oil additive consisting essentially of a mixture of at least one bismuth dihydrocarbyl dithiophosphate and at least one salt selected from the group consisting of zinc dihydrocarbyl dithiophosphates and cadmium dihydrocarbyl dithiophosphates, wherein each hy-drocarbyl group contains from 3 to 15 carbon atoms andwherein the amount of bismuth present is from 5% to 90% by weight of the total bismuth and zinc or cadmium present in the dihydrocarbyl dithiophos-phates.2. A lubricating oil additive as claimed in claim 1 wherein each hydrocarbyl group is an alkyl group containing from 3 to 8 carbon atoms.3. A lubricating oil additive as claimed in claim 1 wherein the amount of bismuth present is from 10% to 60%.4. A lubricating oil additive as claimed in claim 1 when prepared by partially neutralising a member of the group consisting of dihydrocarbyl dithiophosphoric acids and mixtures thereof with a member of the group consisting of bismuth oxide, bismuth hydroxide, a mixture of bismuth oxide and zinc oxide, a mixture of bismuth oxide and zinc hydroxide, a mixture of bismuth hydroxide and zinc oxide, a mixture of bismuth hydroxide and zinc hydroxide, a mixture of bismuth oxide and cadmium hydroxide, a mixture of bismuth oxide and cadmium oxide, a mixture of bismuth hydroxide and cadmuim oxide, and a mixture of bismuth hydroxide and cadmium hydroxide and further reacting the partially neutralised product with a member of the group consisting of zinc oxide, zinc hydroxide, cadmium oxide and cadmium hydroxide to provide a substantially neutral mixture of at least one bismuth dihydrocarbyl dithiophosphate and at least one member of the group consisting of zinc dihydrocarbyl dithiophosphates and cadmium dihydrocarbyl dithiophosphates.5. A lubricating oil additive as claimed in claim 1 consisting essentially of a bismuth dihydrocarbyl dithiophosphate and a zinc dihydrocarbyl dithiophosphate.6. A lubricating oil additive as claimed in claim 5 wherein the amount of bismuth present is from 10% to90% by weight of the total weight of bismuth and zinc present in the dihydrocarbyl dithiophosphate.7. A lubricating oil additive as claimed in claim 5 in admixture with an oil of lubricating viscosity, the additive being admixed with the oil in an amount of from 0.01% to 10% by weight based on the total weight of the oil and additive.8. A lubricating oil additive as claimed in claim 1 in admixture with an oil of lubricating viscosity, the additive being admixed with the oil in an amount of 0.01% to 10% by weight based on the total weight of the oil and additive.9. A lubricating oil additive as claimed in claim 7 admixed with the oil in an amount of from 0.1% to 2% by weight.UNITEDSTATES PATENTS2,506,5705/1950Andress___________2,944,9727/1960Welsh_____________. 2523.290,34712/1966Miller_____________. 2523,428,5632/1969Lowe_____________DANIEL E. WYMAN, Primary Examinerj I. VAUGHN, Assistant ExaminerU.S. Cl. X.R.252—400