US3008900A - Manufacture of mixed nickel and zinc dithiophosphate - Google Patents
Manufacture of mixed nickel and zinc dithiophosphate Download PDFInfo
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- US3008900A US3008900A US753627A US75362758A US3008900A US 3008900 A US3008900 A US 3008900A US 753627 A US753627 A US 753627A US 75362758 A US75362758 A US 75362758A US 3008900 A US3008900 A US 3008900A
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- Prior art keywords
- nickel
- zinc
- mixed
- dithiophosphate
- neutralizing
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 62
- 229910052759 nickel Inorganic materials 0.000 title claims description 31
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- -1 DITHIOPHOSPHORIC ACID DIESTER Chemical class 0.000 claims description 22
- 230000003472 neutralizing effect Effects 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 17
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 22
- 239000003795 chemical substances by application Substances 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 11
- 239000011787 zinc oxide Substances 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 10
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 7
- 239000010687 lubricating oil Substances 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 210000000707 wrist Anatomy 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000010688 mineral lubricating oil Substances 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- HVSYRUKKSFWIKV-UHFFFAOYSA-K dioxido-sulfanylidene-sulfido-lambda5-phosphane nickel(3+) Chemical class [Ni+3].[O-]P([O-])([S-])=S HVSYRUKKSFWIKV-UHFFFAOYSA-K 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000003752 zinc compounds Chemical class 0.000 description 2
- LBZYEJVGHCWCAF-UHFFFAOYSA-K zinc dioxido-sulfanylidene-sulfido-lambda5-phosphane nickel(2+) Chemical compound P(=S)([S-])([O-])[O-].[Zn+2].[Ni+2] LBZYEJVGHCWCAF-UHFFFAOYSA-K 0.000 description 2
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- 241000158728 Meliaceae Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical compound S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- WIKSRXFQIZQFEH-UHFFFAOYSA-N [Cu].[Pb] Chemical compound [Cu].[Pb] WIKSRXFQIZQFEH-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
Definitions
- This invention relates to a novel process for the manufacture of additives particularly suitable for incorporation in mineral oil compositions and more specifically to a process for the manufacture of additives consisting essentially of mixed nickel and zinc dithiophospha-tes.
- each additive agent is employed to impart a particular characteristic to the base oil so as to afiord a finished lubricating composition which is oxidation resistant, stable and non-corrosive to bearing metals, and which effectively reduces varnish and sludge-forming tendencies and minimizes frictional and corrosive wear.
- phosphate can be used in lubricating oils to reduce wrist pin and rocker arm shaft wear. Also, this agent inhibits oxidation and deterioration of the oil without causing ucndue wear to any engine part such as the rocker arm shaft of a valve-in-head engine.
- a nickel compound such as nickel carbonate is reacted with a dithiophosphoric acid diester at a temperature of from about 70 F. to 165 F.
- the resulting material is then reacted with a zinc component such as zinc oxide at a temperature of about 70 F. to 165 F.
- the mixed dithiophosphates are then readily separated by filtration.
- the reaction product is dehydrated until substantially all the water is removed, and a filtering aid can be added to enhance the subsequent filtration.
- Typical inorganic nickel and zinc components which may be utilized in our invention are the salts of inorganic acids, hydroxides and the metals themselves.
- the amount of the nickel component added can range from about 25 to preferably about 40 to 60%, of theory (based on neutralizing the dithiophosphoric acid ester) while the Zinc component employed in the subsequent neutralization can be about 25 to 75% of theory, preferably about 40 to 60%. It is preferred to employ about to 98% of theory of the combined metal components.
- the neutralization steps it is pre- 'ferred to employ low temperatures to avoid undue hydrolysis of the dithiophosphates by any water present, and the same is true as to any dehydration effected after neutralization. Consequently, it may even be desirable to employ a vacuum dehydration procedure.
- the dithiophosphoric acid d-iester may be conventionally prepared by reacting a sulfide of phosphorus such as phosphorus pentasulfide with an alcohol or a phenol.
- Suitable alcohols which may be employed in preparing the acid esters include aromatic or aliphatic alcohols containing from 4 to 12 carbon atoms such as 4-methylpentanol-2, hexanol, heptanol, etc.
- Aromatic alcohols or hydroxyl-containing materials which can be reacted with phosphorus sulfide include phenols and alkylated phenols.
- Optimum results are obtained while using an approximately 50/50 molar ratio of nickel to zinc by first adding nickel carbonate to dithiophosphoric acid diester, such as di-(2-methylpentyl-4)dithiophosphoric acid diester, while maintaining a preferred temperature of about 70 F. to 165 P. Then zinc oxide is slowly added while maintaining a preferred temperature of about 70 F. to 165 F. Next the reaction mixture is dehydrated at a temperature below about 300 F., a filter aid such as Supercel (containing essentially diatomaceous silica) is added and the product is filtered. The resulting product is mixed nickel and zinc dithiophosphate.
- nickel carbonate such as di-(2-methylpentyl-4)dithiophosphoric acid diester
- zinc oxide is slowly added while maintaining a preferred temperature of about 70 F. to 165 F.
- the reaction mixture is dehydrated at a temperature below about 300 F., a filter aid such as Supercel (containing essentially diatomaceous silica) is added and the product
- Example I About 89 grams of nickel carbonate is slowly added while stirring to about 1000 grams of 2-methylpentyl-4 dithiophosphoric acid diester while maintaining a maximum temperature of about 148 F. After all the nickel carbonate is added the reaction is then stirred and heated at about 140 F. for about one hour. The reaction is then cooled slightly and 55 grams of zinc oxide is added While maintaining a maximum temperature of about 150 F. When the addition of the zinc oxide is complete the reaction is dehydrated at about 250 F. for a period of about one hour. Then 20 grams of Supercel is added and the product is filtered. The product a mixed nickel and zinc dithiophosphate analyzes as follows:
- Example II 475 pounds of nickel carbonate is added to 5410 lbs. of 2-methylpentyl-4 dithiophosphoric acid diester during a period of about 1 /2 hours while maintaining a maximum temperature of about 146 F. The reaction is then stirred for about one hour at about 140 F. 325 pounds of zinc oxide is then added over a period of about 3% hours while maintaining a maximum temperature of about 148 F. The temperature is now raised to about 250 F. for a period of approximately one hour then the temperature is lowered to about 215 F. and 100 lbs. of Supercel is added. The product is now filtered. The filtration takes place in a pressure range of from about 30 p.s.i.g. to about 36 p.s.i.:g. Thus a filtration rate of approximately 162 lbs/sq. ft. filter area/hour is obtained.
- the product nickel-zinc dithiophosphate analyzes as follows:
- a process for the manufacture of a mixed nickel and zinc dithiophosphate consisting essentially of reacting at a temperature of about 70 to 165 F., less than the neutralizing stoichiometric amount of a neutralizing inorganic nickel component with a dithiophosphoric acid diester of an alcohol of from 4 to 12 carbon atoms to partially neutralize the acid ester and obtain an intermediate reaction product, reacting at a temperature of about 70 to 165 F. a neutralizing inorganic zinc component with the intermediate reaction product to further neutralize the acid ester and obtain a mixed nickel and zinc dithiophosphate and filtering to separate the mixed dithiophosphate, the amounts of each of said nickel and zinc components being about 25 to 75 percent of theory based on the dithiophosphoric acid diester.
- a process for the manufacture of a mixed nickel and zinc dithiophosphate consisting essentially of reacting, at a temperature of about 70 to F., less than the neutralizing stoichiometric amount of a neutralizing inorganic nickel component with a dithiophosphoric acid diester of an alcohol of from 4 to 12 carbon atoms to partially neutralize the acid ester and obtain an intermediate reaction product, reacting at a temperature of about 70 to 165 F.
- a neutralizing inorganic zinc component with the intermediate reaction product to further neutralize the acid ester and obtain a mixed nickel and zinc dithiophosphate and filtering to separate the mixed dithiophosphate, each of said nickel and zinc components being employed in amounts from about 25 to 75 percent of theory based on the dithiophosphoric acid diester and being selected from the group consisting of the nickel and zinc salts of inorganic acids, oxides, hydroxides, and the metals themselves.
- a process for the manufacture of a mixed nickel and zinc dithiophosphate consisting essentially of reacting, at a temperature of about 70 to 165 F., less than the neutralizing stoichiometric amount of a neutralizing inorganic nickel compound with a dithiophosphoric acid diester of an alcohol of from 4 to 12 carbon atoms to partially neutralize the acid ester and obtain an intermediate reaction product, reacting at a temperature of about 70 to 165 F.
- a neutralizing inorganic zinc compound with the intermediate reaction product to further neutralize the acid ester and obtain a mixed nickel and zinc dithiophosphate and filtering to separate the mixed dithiophosphate, the amounts of each of said nickel and zinc compounds being about 25 to 75 percent of theory based on the dithiophosphoric acid diester.
- a process for the manufacture of a mixed nickel and zinc dithiophosphate consisting essentially of reacting, at a temperature of about 70 to 165 F., less than the neutralizing stoichiometric amount of neutralizing nickel carbonate with a dithiophosphoric acid diester of an alcohol of from 4 to 12 carbon atoms to partially neutralize the acid ester and obtain an intermediate reaction product, reacting, at a temperature of about 70 to 165 F neutralizing zinc oxide with the intermediate reaction product to further neutralize the acid ester and obtain a mixed nickel and zinc dithiophosphate, dehydrating the mixed dithiophosphate, and filtering to separate the mixed dithiophosphate, the amounts of each said nickel carbonate and zinc oxide being about 25 to 75 percent of theory based on the dithiophosphoric acid diester.
- a process for the manufacture of a mixed nickel and zinc dithiophosphate consisting essentially of reacting at a temperature of about 70 to 165 F. less than the neutralizing stoichiometric amount of a neutralizing nickel carbonate with a dithiophosphoric acid diester of an alcohol of from 4 to 12 carbon atoms to partially neutralize the acid ester and obtain an intermediate reaction product, reacting at a temperature of about 70 to 165 F. a neutralizing zinc oxide with the intermediate reaction product to further neutralize the acid ester and obtain a mixed nickel and zinc dithiophosphate and dehydrating and filtering to separate the mixed dithiophosphate, the amounts of each of said nickel carbonate and zinc oxide being about 40 to 60 percent of theory based on the dithiophosphoric acid diester.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Lubricants (AREA)
Description
tates This invention relates to a novel process for the manufacture of additives particularly suitable for incorporation in mineral oil compositions and more specifically to a process for the manufacture of additives consisting essentially of mixed nickel and zinc dithiophospha-tes.
With the advent of higher compression internal combustion engines and increases in horsepower, much difficulty has been experienced in formulating a suitable oil composition capable of operating under severe conditions to protect efficiently metal surfaces which come in contact with the oil. In an effort to overcome this problem, a wide variety of additive agents such as detergents, antioxidants, anti-wear agents and the like have been proposed for the improvement of lubricating oils. Generally, each additive agent is employed to impart a particular characteristic to the base oil so as to afiord a finished lubricating composition which is oxidation resistant, stable and non-corrosive to bearing metals, and which effectively reduces varnish and sludge-forming tendencies and minimizes frictional and corrosive wear.
Unfortunately, however, while many of the proposed additive agents improve mineral lubricating oils, quite frequently these lubricating oil compositions have not proved to be entirely satisfactory for commercial use since apparently an additive agent which imparts a beneficial effect may impart unpredictable and undesirable wear to a given engine part. For example, a small amount of zinc dithiophosph-ate displays satisfactory oxidation and bearing corrosion inhibiting properties in a mineral lubricating oil. This additive is particularly active in reducing the corrision of copper-lead bearings subjected to severe operating conditions of temperature and pressure. However, a lubricating oil containing a zinc dithiophosphate and a detergent type agent such as for example, basic barium mahogany sulfonate, was found to allow excessive wear of parts such as wrist pins, valvelifters and rocker arm shafts in recent models of valve-in-head engines. Elimination of the zinc dithiophosphate reduced wrist pin and rocker arm shaft wear but, of course, the resulting composition was subject to oxidative deterioration and the bad effects derived therefrom. The subsequent addition of an anti-wear agent such as sulfurized sperm oil to the composition containing the zinc dithiophosphate for practical purposes eliminated wrist pin wear and reduced valve lifter wear but did not solve the rocker arm shaft wear problems. In fact, the antiwear agent increased rocker arm shaft wear of the base mineral oil. Thus both the zinc dithiophosphate and the anti-wear agent caused excessive wear of the rocker arm shaft and as a result this compounded oil had undesirable,
properties. Such has been the case when using many additive agents and hence much difiiculty has been experienced in formulating an engine lubricating oil of satisfactory anti-wear and anti-oxidant properties.
While displaying satisfactory oxidation and bearing corrosion inhibiting properties in mineral lubricating oils, nickel dithiophosphates have not proved entirely satisfactory for commercial applications since apparently the nickel salt allows spalling of the valve lifters. Thus the problem of discovering a satisfactory lubricating oil composition containing the desired corrosion properties without causing wear to wrist pin and valve lifter has long been a source of experimentation and observation.
Patented Nov. 14, 1961 In the present invention We have discovered a novel method of preparing an additive which may be used in mineral lubricating oil compositions, namely a mixed nickel and zinc dithiophosphate. If less than the stoichiometric amount of an inorganic nickel component such as nickel carbonate is added to a dithiophosphoric acid diester and the resulting material is reacted with an inorganic zin-c component such as zinc or zinc oxide a mixed nickel-zinc dithiophosphate is formed. By this initial addition of the nickel component and the subsequent addition of the zinc component substantially superior filtration rates can be obtained. The mixed nickel and zinc dithiophosphates are easily filtered and optimum filtration rates can be maintained over reasonable periods of time. phosphate can be used in lubricating oils to reduce wrist pin and rocker arm shaft wear. Also, this agent inhibits oxidation and deterioration of the oil without causing ucndue wear to any engine part such as the rocker arm shaft of a valve-in-head engine.
In the present invention a nickel compound such as nickel carbonate is reacted with a dithiophosphoric acid diester at a temperature of from about 70 F. to 165 F. The resulting material is then reacted with a zinc component such as zinc oxide at a temperature of about 70 F. to 165 F. The mixed dithiophosphates are then readily separated by filtration. Preferably, prior to the filtration the reaction product is dehydrated until substantially all the water is removed, and a filtering aid can be added to enhance the subsequent filtration. Typical inorganic nickel and zinc components which may be utilized in our invention are the salts of inorganic acids, hydroxides and the metals themselves. In the initial neutralization step the amount of the nickel component added can range from about 25 to preferably about 40 to 60%, of theory (based on neutralizing the dithiophosphoric acid ester) while the Zinc component employed in the subsequent neutralization can be about 25 to 75% of theory, preferably about 40 to 60%. It is preferred to employ about to 98% of theory of the combined metal components. In the neutralization steps it is pre- 'ferred to employ low temperatures to avoid undue hydrolysis of the dithiophosphates by any water present, and the same is true as to any dehydration effected after neutralization. Consequently, it may even be desirable to employ a vacuum dehydration procedure.
The dithiophosphoric acid d-iester may be conventionally prepared by reacting a sulfide of phosphorus such as phosphorus pentasulfide with an alcohol or a phenol. Suitable alcohols which may be employed in preparing the acid esters include aromatic or aliphatic alcohols containing from 4 to 12 carbon atoms such as 4-methylpentanol-2, hexanol, heptanol, etc. Aromatic alcohols or hydroxyl-containing materials which can be reacted with phosphorus sulfide include phenols and alkylated phenols.
The following data show the various filtration rates obtained in the preparation of dithiophosphates which may be used as additives in lubricating oils.
TABLE I RunNo 3 I 4 Percent 1 NiCOa Percent ZnO Filtration Rate (lbs./ft. /hr.)
The above data clearly indicate that mixed nickel-zinc The resulting mixed nickel and zinc dithiodithiophosphates may be produced at a much more rapid rate than nickel dithiophosphate due to the elimination of the filtration difiiculties associated with the nickel salt.
Optimum results are obtained while using an approximately 50/50 molar ratio of nickel to zinc by first adding nickel carbonate to dithiophosphoric acid diester, such as di-(2-methylpentyl-4)dithiophosphoric acid diester, while maintaining a preferred temperature of about 70 F. to 165 P. Then zinc oxide is slowly added while maintaining a preferred temperature of about 70 F. to 165 F. Next the reaction mixture is dehydrated at a temperature below about 300 F., a filter aid such as Supercel (containing essentially diatomaceous silica) is added and the product is filtered. The resulting product is mixed nickel and zinc dithiophosphate.
The following specific examples are not to be considered limiting.
Example I About 89 grams of nickel carbonate is slowly added while stirring to about 1000 grams of 2-methylpentyl-4 dithiophosphoric acid diester while maintaining a maximum temperature of about 148 F. After all the nickel carbonate is added the reaction is then stirred and heated at about 140 F. for about one hour. The reaction is then cooled slightly and 55 grams of zinc oxide is added While maintaining a maximum temperature of about 150 F. When the addition of the zinc oxide is complete the reaction is dehydrated at about 250 F. for a period of about one hour. Then 20 grams of Supercel is added and the product is filtered. The product a mixed nickel and zinc dithiophosphate analyzes as follows:
Percent nickel 3.95 Percent zinc 4.43 Percent phosphorus 9.67 Percent sulfur 19.2
Example II 475 pounds of nickel carbonate is added to 5410 lbs. of 2-methylpentyl-4 dithiophosphoric acid diester during a period of about 1 /2 hours while maintaining a maximum temperature of about 146 F. The reaction is then stirred for about one hour at about 140 F. 325 pounds of zinc oxide is then added over a period of about 3% hours while maintaining a maximum temperature of about 148 F. The temperature is now raised to about 250 F. for a period of approximately one hour then the temperature is lowered to about 215 F. and 100 lbs. of Supercel is added. The product is now filtered. The filtration takes place in a pressure range of from about 30 p.s.i.g. to about 36 p.s.i.:g. Thus a filtration rate of approximately 162 lbs/sq. ft. filter area/hour is obtained. The product nickel-zinc dithiophosphate analyzes as follows:
Percent nickel 3.76 Percent zinc 4.87 Percent sulfur 17.3 Percent phosphorus 9.60
We claim:
1. A process for the manufacture of a mixed nickel and zinc dithiophosphate consisting essentially of reacting at a temperature of about 70 to 165 F., less than the neutralizing stoichiometric amount of a neutralizing inorganic nickel component with a dithiophosphoric acid diester of an alcohol of from 4 to 12 carbon atoms to partially neutralize the acid ester and obtain an intermediate reaction product, reacting at a temperature of about 70 to 165 F. a neutralizing inorganic zinc component with the intermediate reaction product to further neutralize the acid ester and obtain a mixed nickel and zinc dithiophosphate and filtering to separate the mixed dithiophosphate, the amounts of each of said nickel and zinc components being about 25 to 75 percent of theory based on the dithiophosphoric acid diester.
2. A process for the manufacture of a mixed nickel and zinc dithiophosphate consisting essentially of reacting, at a temperature of about 70 to F., less than the neutralizing stoichiometric amount of a neutralizing inorganic nickel component with a dithiophosphoric acid diester of an alcohol of from 4 to 12 carbon atoms to partially neutralize the acid ester and obtain an intermediate reaction product, reacting at a temperature of about 70 to 165 F. a neutralizing inorganic zinc component with the intermediate reaction product to further neutralize the acid ester and obtain a mixed nickel and zinc dithiophosphate and filtering to separate the mixed dithiophosphate, each of said nickel and zinc components being employed in amounts from about 25 to 75 percent of theory based on the dithiophosphoric acid diester and being selected from the group consisting of the nickel and zinc salts of inorganic acids, oxides, hydroxides, and the metals themselves.
3. A process for the manufacture of a mixed nickel and zinc dithiophosphate consisting essentially of reacting, at a temperature of about 70 to 165 F., less than the neutralizing stoichiometric amount of a neutralizing inorganic nickel compound with a dithiophosphoric acid diester of an alcohol of from 4 to 12 carbon atoms to partially neutralize the acid ester and obtain an intermediate reaction product, reacting at a temperature of about 70 to 165 F. a neutralizing inorganic zinc compound with the intermediate reaction product to further neutralize the acid ester and obtain a mixed nickel and zinc dithiophosphate and filtering to separate the mixed dithiophosphate, the amounts of each of said nickel and zinc compounds being about 25 to 75 percent of theory based on the dithiophosphoric acid diester.
4. A process for the manufacture of a mixed nickel and zinc dithiophosphate consisting essentially of reacting, at a temperature of about 70 to 165 F., less than the neutralizing stoichiometric amount of neutralizing nickel carbonate with a dithiophosphoric acid diester of an alcohol of from 4 to 12 carbon atoms to partially neutralize the acid ester and obtain an intermediate reaction product, reacting, at a temperature of about 70 to 165 F neutralizing zinc oxide with the intermediate reaction product to further neutralize the acid ester and obtain a mixed nickel and zinc dithiophosphate, dehydrating the mixed dithiophosphate, and filtering to separate the mixed dithiophosphate, the amounts of each said nickel carbonate and zinc oxide being about 25 to 75 percent of theory based on the dithiophosphoric acid diester.
5. A process for the manufacture of a mixed nickel and zinc dithiophosphate consisting essentially of reacting at a temperature of about 70 to 165 F. less than the neutralizing stoichiometric amount of a neutralizing nickel carbonate with a dithiophosphoric acid diester of an alcohol of from 4 to 12 carbon atoms to partially neutralize the acid ester and obtain an intermediate reaction product, reacting at a temperature of about 70 to 165 F. a neutralizing zinc oxide with the intermediate reaction product to further neutralize the acid ester and obtain a mixed nickel and zinc dithiophosphate and dehydrating and filtering to separate the mixed dithiophosphate, the amounts of each of said nickel carbonate and zinc oxide being about 40 to 60 percent of theory based on the dithiophosphoric acid diester.
6. The method of claim 5 in which the diester is di- (2-methylpentyl-4)-dithiophosphoric acid diester.
References Cited in the file of this patent UNITED STATES PATENTS 2,344,392 Cook et al. Mar. 14, 1944 2,413,332 Musselman Dec. 31, 1946 2,441,587 Musselman May 18, 1948 2,582,958 Brennan et al. Jan. 22, 1952 2,606,872 Gasser et al. Aug. 12, 1952 2,645,613 Adelson et al. July 14, 1953 2,824,063 Verley Feb. 18, 1958
Claims (1)
1. A PROCESS FOR THE MANUFACTURE OF A MIXED NICKEL AND ZINC DITHIOPHOSPHATE CONSISTING ESSENTIALLY OF REACTING AT A TEMPERATURE OF ABOUT 70* TO 165*F., LESS THAN THE NEUTRALIZING STOICHIOMETRIC AMOUNT OF A NEUTRALIZING INORGANIC NICKEL COMPONENT WITH A DITHIOPHOSPHORIC ACID DIESTER OF AN ALCOHOL OF FROM 4 TO 12 CARBON ATOMS TO PARTIALLY NEUTRALIZE THE ACID ESTER AND OBTAIN AN INTERMEDIATE REACTION PRODUCT, REACTING AT A TEMPERATURE OF ABOUT 70* TO 165*F. A NEUTRALIZING INORGANIC ZINC COMPONENT WITH THE INTERMEDIATE REACTION PRODUCT TO FURTHER NEUTRALIZE THE ACID ESTER AND OBTAIN A MIXED NICKEL AND ZINC DITHIOPHOSPHATE AND FILTERING TO SEPARATE THE MIXED DITHIOPHOSPHATE, THE AMOUNTS OF EACH OF SAID NICKEL AND ZINC COMPONENTS BEING ABOUT 25 TO 75 PERCENT OF THEORY BASED ON THE DITHIOPHOSPHORIC ACID DIESTER.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US753627A US3008900A (en) | 1958-08-07 | 1958-08-07 | Manufacture of mixed nickel and zinc dithiophosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US753627A US3008900A (en) | 1958-08-07 | 1958-08-07 | Manufacture of mixed nickel and zinc dithiophosphate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3008900A true US3008900A (en) | 1961-11-14 |
Family
ID=25031467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US753627A Expired - Lifetime US3008900A (en) | 1958-08-07 | 1958-08-07 | Manufacture of mixed nickel and zinc dithiophosphate |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3008900A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3290347A (en) * | 1963-02-28 | 1966-12-06 | Exxon Research Engineering Co | Preparation of polyvalent metal salts of diorgano dithiophosphoric acids |
| US4123370A (en) * | 1977-05-19 | 1978-10-31 | The Lubrizol Corporation | Preparation and use of basic metal salt compositions of phosphorus-containing acids |
| EP0318218A3 (en) * | 1987-11-24 | 1990-03-21 | Exxon Chemical Patents Inc. | Dihydrocarbyl dithiophosphates |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2344392A (en) * | 1941-11-08 | 1944-03-14 | American Cyanamid Co | Crankcase lubricant and chemical compound therefor |
| US2413332A (en) * | 1943-12-15 | 1946-12-31 | Standard Oil Co | Composition of matter suitable for use as a lubricant and lubricant comprising the same |
| US2441587A (en) * | 1944-07-25 | 1948-05-18 | Standard Oil Co | Method of preparing composition of matter suitable for use as a lubricant and as an addition agent to lubricants |
| US2582958A (en) * | 1948-10-16 | 1952-01-22 | Pure Oil Co | Detergent oil composition and the method for its preparation |
| US2606872A (en) * | 1948-12-06 | 1952-08-12 | Shell Dev | Lubricating composition |
| US2645613A (en) * | 1949-03-14 | 1953-07-14 | Shell Dev | Lubricating composition |
| US2824063A (en) * | 1956-05-11 | 1958-02-18 | Sinclair Refining Co | Lubricating oils containing a zinc dithiophosphate and nickel mahogany sulfonate |
-
1958
- 1958-08-07 US US753627A patent/US3008900A/en not_active Expired - Lifetime
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2344392A (en) * | 1941-11-08 | 1944-03-14 | American Cyanamid Co | Crankcase lubricant and chemical compound therefor |
| US2413332A (en) * | 1943-12-15 | 1946-12-31 | Standard Oil Co | Composition of matter suitable for use as a lubricant and lubricant comprising the same |
| US2441587A (en) * | 1944-07-25 | 1948-05-18 | Standard Oil Co | Method of preparing composition of matter suitable for use as a lubricant and as an addition agent to lubricants |
| US2582958A (en) * | 1948-10-16 | 1952-01-22 | Pure Oil Co | Detergent oil composition and the method for its preparation |
| US2606872A (en) * | 1948-12-06 | 1952-08-12 | Shell Dev | Lubricating composition |
| US2645613A (en) * | 1949-03-14 | 1953-07-14 | Shell Dev | Lubricating composition |
| US2824063A (en) * | 1956-05-11 | 1958-02-18 | Sinclair Refining Co | Lubricating oils containing a zinc dithiophosphate and nickel mahogany sulfonate |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3290347A (en) * | 1963-02-28 | 1966-12-06 | Exxon Research Engineering Co | Preparation of polyvalent metal salts of diorgano dithiophosphoric acids |
| US4123370A (en) * | 1977-05-19 | 1978-10-31 | The Lubrizol Corporation | Preparation and use of basic metal salt compositions of phosphorus-containing acids |
| EP0318218A3 (en) * | 1987-11-24 | 1990-03-21 | Exxon Chemical Patents Inc. | Dihydrocarbyl dithiophosphates |
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