US3654329A - Zinc dithiophosphates - Google Patents
Zinc dithiophosphates Download PDFInfo
- Publication number
- US3654329A US3654329A US780906A US3654329DA US3654329A US 3654329 A US3654329 A US 3654329A US 780906 A US780906 A US 780906A US 3654329D A US3654329D A US 3654329DA US 3654329 A US3654329 A US 3654329A
- Authority
- US
- United States
- Prior art keywords
- zinc
- dithiophosphate
- butyl
- tert
- additives
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical class [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 title description 12
- 239000011701 zinc Chemical group 0.000 abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052725 zinc Chemical group 0.000 abstract description 6
- -1 HYDROXY GROUP Chemical group 0.000 abstract description 5
- 239000003963 antioxidant agent Substances 0.000 abstract description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052788 barium Inorganic materials 0.000 abstract description 4
- 229910052793 cadmium Inorganic materials 0.000 abstract description 4
- 229910052791 calcium Inorganic materials 0.000 abstract description 4
- 239000011575 calcium Substances 0.000 abstract description 4
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 235000006708 antioxidants Nutrition 0.000 abstract description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical group [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical group [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 239000000654 additive Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 125000003143 4-hydroxybenzyl group Chemical group [H]C([*])([H])C1=C([H])C([H])=C(O[H])C([H])=C1[H] 0.000 description 2
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- XDFCIPNJCBUZJN-UHFFFAOYSA-N barium(2+) Chemical compound [Ba+2] XDFCIPNJCBUZJN-UHFFFAOYSA-N 0.000 description 2
- RDVQTQJAUFDLFA-UHFFFAOYSA-N cadmium Chemical compound [Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd][Cd] RDVQTQJAUFDLFA-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241001558496 Talpa caeca Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000006289 hydroxybenzyl group Chemical group 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
- C10M137/10—Thio derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/02—Groups 1 or 11
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/08—Groups 4 or 14
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/10—Groups 5 or 15
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/14—Group 7
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/16—Groups 8, 9, or 10
Definitions
- R0 OR" RO OR wherein M is calcium, barium, nickel, cadmium, lead or zinc and R, R, R" and R are substituted or unsubstituted hydrocarbon radicals, at least one having the formula:
- A is a bivalent hydrocarbon radical and n is zero or a whole number from 1 to 20 and at least one of said R R R R and R groups is a hydroxy group sterically hindered by another of said groups which is an alkyl group.
- the remaining groups are hydrogen or alkyl.
- This invention relates to novel compounds which are suitable as anti-oxidant additives for lubricants, and to lubricants containing these compounds.
- zinc dialkyldithiophosphates are used as additives for lubricating oils on account of the fact that these compounds impart to the lubricants to which they are added a strong resistance against oxidation, as well as anti wear and anti-corrosion properties.
- an anti-oxidant additive for a lubricating oil a compound represented by the following general formula:
- RIO OR!!! wherein M is a calcium, barium, nickel, cadmium, lead or zinc atom, and R, R, R" and R' are substituted or unsubstituted hydrocarbon radicals, at least one of R, R, R, R
- A is non-existent or is a bivalent hydrocarbon radical containing from 1 to carbon atoms and optionally containing an ether, ester or thioether group, at least one of the radicals R R R R and R isa hydroxyl group,
- At least one other of the radicals R R R R and R is an alkyl group which sterically hinders the said hydroxyl group, and each of the remainder of the radicals R R R R and R is a primary, secondary or tertiary alkyl group or a hydrogen atom.
- A is a bivalent hydrocarbon radical containing from 2 to 10 carbon atoms.
- the alkyl radical which sterically hinders the hydroxyl group is a secondary or tertiary alkyl group.
- alkyl radicals having a steric hindrance on the hydroxyl, which are in a vicinal position with respect to the hydroxyl.
- suitable radicals for this purpose include t.-butyl, dirnethyl-ethyl-methyl, methyldiethylmethyl, triethylmethyl, isopropyl and sbutyl.
- the products of this invention possess approximately the anti wear and anti-corrosion properties found in the zinc dithiophosphates obtained from n-alcohols.
- the metal dithiophosphates of the invention may be obtained by reacting P 5 and the appropriate alcohol or alcohols in the approximate molar ratio of 1:4, at an elevated temperature, generally at a temperature of from 50 C. to 200 C., preferably from C. to 120 C., and then neutralizing the resulting dithiophosphate acid with a metallic oxide, for example zinc oxide.
- the infrared spectrographic analysis of the product confirmed the presence of a dithiophosphate group.
- the comparative additives were selected 8'82 32 gg from zinc dithiophosphates obtained from aliphatic 0:03 2: Do: alcohols and mixtures thereof with 2,6-di-tert.butyl-para- 8'83 i h g' cresol in equimolar concentrations based on the additives 0:03 2:95 Slight. of the invention.
- the zinc dithiophosphates of the invention have a high anti-oxidant activity, and the synergism existing between the dialkyl zinc dithiophosphates and sterically hindered phenols, increases when the sterically hindered phenol forms part of the dithiophosphate molecule.
- A is the additive of the Example 1
- B the additive of the Example 2
- C the additive of the EX- ample 3
- D the additive of the EX- ample 3
- D the additive of the EX- ample 3
- E and F are different known commercial additives based on Zinc dithiophosphates. The tests were carried out with a Shell 4 ball Wear Tester, each test lasting 60 seconds at a speed of 1200 r.p.m.
- the additives of the invention generally have a better anti-rust characteristic than known additives.
- M is a calcium, barium, nickel, cadmium, lead or zinc atom; and R, R, R" and R' are alkyl radicals containing up to 10 carbons, at least one of R, R, R" and R having the formula:
- a compound as claimed in claim 1 wherein said hydroxy group is sterically hindered by vicinally positioned secondary or tertiary alkyl groups.
- a compound as claimed in claim 1 wherein said hydroxy group is in the para position sterically hindered by vicinally positioned tertiary butyl groups.
- a compound as claimed in claim 1 having the name bis[( 3,5 di-tert.butyl-4-hydroxy-benzy1)propyl] zinc dithiophosphate.
- a compound as claimed in claim 1 having the name (4 methyl -2- pentyl) [(3,S-di-tert.butyl-4-hydroxy-benzyl)-propyl] zinc dithiophosphate.
- a compound as claimed in claim 1 having the name cetyl[(3,5 di tert.buty1-4-hydroxy-benzyl)-propyl] zinc dithiophosphate.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Lubricants (AREA)
Abstract
ANTI-OXIDANTS ARE DISCLOSED HAVING THE FORMULA:
R-O-P(-O-R'')(=S)-S-M-S-P(=S)(-O-R")-O-R"''
WHEREIN M IS CALCIUM, BARIUM, NICKEL, CADMIUM, LEAD OR ZINC AND R, R'', R" AND R"'' ARE SUBSTITUTED OR UNSUBSTITUTED HYDROCARBON RADICALS, AT LEAST ONE HAVING THE FORMULA:
(2-R2,3-R1,4-R3,5-R4,5-R5-PHENYL)-(A)N-
WHEREIN A IS A BIVALENT HYDROCARBON RADICAL AND N IS ZERO OR A WHOLE NUMBER FROM 1 TO 20 AND AT LEAST ONE OF SAID R1, R2, R3, R4 AND R5 GROUPS IS A HYDROXY GROUP STERICALLY HINDERED BY ANOTHER OF SAID GROUPS WHICH IS AN ALKYL GROUP. THE REMAINING GROUPS ARE HYDROGEN OR ALKYL.
R-O-P(-O-R'')(=S)-S-M-S-P(=S)(-O-R")-O-R"''
WHEREIN M IS CALCIUM, BARIUM, NICKEL, CADMIUM, LEAD OR ZINC AND R, R'', R" AND R"'' ARE SUBSTITUTED OR UNSUBSTITUTED HYDROCARBON RADICALS, AT LEAST ONE HAVING THE FORMULA:
(2-R2,3-R1,4-R3,5-R4,5-R5-PHENYL)-(A)N-
WHEREIN A IS A BIVALENT HYDROCARBON RADICAL AND N IS ZERO OR A WHOLE NUMBER FROM 1 TO 20 AND AT LEAST ONE OF SAID R1, R2, R3, R4 AND R5 GROUPS IS A HYDROXY GROUP STERICALLY HINDERED BY ANOTHER OF SAID GROUPS WHICH IS AN ALKYL GROUP. THE REMAINING GROUPS ARE HYDROGEN OR ALKYL.
Description
United States Patent US. Cl. 260-4299 6 Claims ABSTRACT OF THE DISCLOSURE Anti-oxidants are disclosed having the formula:
R0 OR" RO OR wherein M is calcium, barium, nickel, cadmium, lead or zinc and R, R, R" and R are substituted or unsubstituted hydrocarbon radicals, at least one having the formula:
a B4 Rs wherein A is a bivalent hydrocarbon radical and n is zero or a whole number from 1 to 20 and at least one of said R R R R and R groups is a hydroxy group sterically hindered by another of said groups which is an alkyl group. The remaining groups are hydrogen or alkyl.
This invention relates to novel compounds which are suitable as anti-oxidant additives for lubricants, and to lubricants containing these compounds.
It is known that zinc dialkyldithiophosphates are used as additives for lubricating oils on account of the fact that these compounds impart to the lubricants to which they are added a strong resistance against oxidation, as well as anti wear and anti-corrosion properties.
It is also known that sterically hindered phenol compounds, for example 2,6-di-t.-butylparacresol, are commonly employed as anti-oxidant additives. In addition, it is known that some mixtures of zinc dialkyldithiophosphates and sterically hindered phenols, impart to the lubricant a high resistance to oxidation because of the synergism existing between those two classes of additives.
According to the present invention, there is provided as an anti-oxidant additive for a lubricating oil a compound represented by the following general formula:
RIO OR!!! wherein M is a calcium, barium, nickel, cadmium, lead or zinc atom, and R, R, R" and R' are substituted or unsubstituted hydrocarbon radicals, at least one of R, R, R
and R' having the following general formula:
where A is non-existent or is a bivalent hydrocarbon radical containing from 1 to carbon atoms and optionally containing an ether, ester or thioether group, at least one of the radicals R R R R and R isa hydroxyl group,
Patented Apr. 4, 1972 at least one other of the radicals R R R R and R is an alkyl group which sterically hinders the said hydroxyl group, and each of the remainder of the radicals R R R R and R is a primary, secondary or tertiary alkyl group or a hydrogen atom.
Preferably A is a bivalent hydrocarbon radical containing from 2 to 10 carbon atoms. Advantageously, the alkyl radical which sterically hinders the hydroxyl group is a secondary or tertiary alkyl group.
Preferably, there are two alkyl radicals having a steric hindrance on the hydroxyl, which are in a vicinal position with respect to the hydroxyl. Examples of suitable radicals for this purpose include t.-butyl, dirnethyl-ethyl-methyl, methyldiethylmethyl, triethylmethyl, isopropyl and sbutyl. The products of this invention possess approximately the anti wear and anti-corrosion properties found in the zinc dithiophosphates obtained from n-alcohols.
The metal dithiophosphates of the invention may be obtained by reacting P 5 and the appropriate alcohol or alcohols in the approximate molar ratio of 1:4, at an elevated temperature, generally at a temperature of from 50 C. to 200 C., preferably from C. to 120 C., and then neutralizing the resulting dithiophosphate acid with a metallic oxide, for example zinc oxide.
The invention will now be illustrated by the following examples.
EXAMPLE 1 Preparation of bis [(3,5-di-tert.-butyl-,4-hydroxy-benzyl) propyl] zinc dithiophosphate 0.4 mole (3,S-di-tert.butyl-,4-hydroxy-benzyl)-propanol were reacted with 0.1 mole of P 8 suspended in benzene at the boiling point of benzene. The reaction was over after about an hour. The benzene was filtered and distilled off under reduced pressure. The resulting dithiophosphoric acid was heated with ZnO in the presence of an inert solvent which forms an azeotrope with water, in this case toluene, in order to neutralize the product. Then the inert solvent was evaporated off and a solid, resinous, orange yellow coloured product was obtained in a yield of Analysis of the product gave the following results:
Calculated (percent): P, 4.73; Zn, 4.99; S, 9.80. Found (percent): P, 4.6; Zn, 4.8; S, 9.9.
Infrared spectrographic analysis confirmed the presence of a dithiophosphate group.
EXAMPLE 2 Preparation of 4-methyl-2-pentyl) [(3,5-di-tert.butyl- 4-hydroxy-benzyl)-propyl] zinc dithiophosphate A mixture of 0.2 mole (3,5-di-tert.butyl-4-hydroxybenzyl)-propanol and 0.2 mole 4-methyl-2-pentanol were allowed to react with 0.1 mole of P 8 under the same conditions as in Example 1, and the product was similarly neutralized with Z to form a liquid, viscous, brownorange coloured product in a yield of 97%.
Analysis of the final product gave the following results:
Calculated (percent): P, 6.29; Zn, 6.63; S, 13.02. Found (percent): P, 6.3; Zn, 6.3; S, 13.3.
Infrared spectrographic analysis confirmed the presence of a dithiophosphate group.
EXAMPLE 3 Preparation of the cetyl [(3,5-di-tert.butyl-4-hydroxylbenzyl)-propyl] zinc dithiophosphate A mixture of 0.1 mole of (3,5-di-tert.butyl-4-hydroxybenzyl)-propanol and of 0.3 mole cetyl alcohol was allowed to react with 0.1 mole of P 5 in a manner similar to that described in Example 1. After neutralization with zinc oxide, a solid, waxy yellow orange coloured product was obtained in a yield of 96%.
Analysis of this product gave the following results:
Calculated (percent): P, 4.98; Zn, 5.25; S, 10.31. Found (percent): P, 4.8; Zn, 5.1; S, 10.4.
The infrared spectrographic analysis of the product confirmed the presence of a dithiophosphate group.
EXAMPLE 4 Evaluation of the anti-oxidant properties The Staeger oxidation test was carried out on a SAE 30 parafiinic mineral oil with a high viscosity index containing the products of this invention or other additives and the results are shown in the following Table 1.
From Table 2, it can be seen that the additives of the invention have anti-wear characteristics of a similar nature The test consisted in heating in a thermostatic stove maintained at 110 C. the oil containing the additives to known addmves' under examination. A strip of electrolytic copper was EXAMPLE 6 immersed in the oil to act as an oxidation catalyst. At Amirust test regular intervals the variation 1n the neutralization number, based on the weight in mg. of KOH./g. oil was 2 In the following Table 3 there are reported the results recorded. found in tests on the anti-rust characteristics of oils con- The test was considered completed when there wa an taining the same additives as Table 2. The tests were carincrement of 0.25 in the neutralization number. Oxidaried out according to the method ASTM/ D 665-54. tion tests were also carried out at 150 C. in the same way as those at 110 C. The concentration of the addi- TABLE 3 tives according to the invention was constant in each Concen- Base oil, case. The content of phosphorus was 44. 10 g. percent, Additive ggf gg si- 1 Rust grade correspondmg to 0.7 millrmole of dlthiophosphate per kg. of solution. The comparative additives were selected 8'82 32 gg from zinc dithiophosphates obtained from aliphatic 0:03 2: Do: alcohols and mixtures thereof with 2,6-di-tert.butyl-para- 8'83 i h g' cresol in equimolar concentrations based on the additives 0:03 2:95 Slight. of the invention.
TABLE 1 Oxidation Oxidation (hours at (hours at 150 necessary to necessary to have an have an Cone. increase of the increase of the (m. mole/ neutralization neutralization kg. of number of number of Additive in SAE 30 mineral oil solution) 0.25) 0.25)
None. 310 Zn bisbutyldithiophosphate 0. 7 810 Bis 1 methyl-2-pentyl) Zn dithiophosphate, 0. 7 1, 120 BiS-cctyl Zn dithiophosphate 0. 7 820 Bis-butyl Zn dithiophosphate 0. 7 1,350 250 2,6di-tert.butyl paracresol 2. 8 Bis[(3,5-di-tert.butyl-,4-hydroxybenzy1)- propyllZn dithiophosphate 0. 7 1, 610 370 Bis(4-methyl-2-pentyl)Zn dithiophosphatc. 0. 7 1, 260 210 2,fi-di-tert.butylparacresol 1, 4 (4-methyl-2-pentyl)-[(3,5-di-tcrt.butyl-,4-
hydroxy-benzyl)-propyl]Zn dithiophosphate 0. 7 l, 420 230 Bis-cetyl Zn dithiophosphate 0. 7 l, 250 270 2,6-di-tert.butylparaercsol O, 7 cetyl [(3,5-di-tert.butyl-4-hydroxybenzyl)- plopyllZn dithiophosphate 0. 7 1,320 300 As can be seen from the oxidation tests recorded in Table 1, the zinc dithiophosphates of the invention have a high anti-oxidant activity, and the synergism existing between the dialkyl zinc dithiophosphates and sterically hindered phenols, increases when the sterically hindered phenol forms part of the dithiophosphate molecule.
EXAMPLE 5 Anti-wear tests In the following Table 2, there are shown the results found in tests in tests on the anti-wear characteristics of an oil containing the products of this invention, compared with the same oil containing known commercial additives.
In Table 2, A is the additive of the Example 1, B the additive of the Example 2, C the additive of the EX- ample 3 and D, E and F are different known commercial additives based on Zinc dithiophosphates. The tests were carried out with a Shell 4 ball Wear Tester, each test lasting 60 seconds at a speed of 1200 r.p.m.
Thus, as can be seen, the additives of the invention generally have a better anti-rust characteristic than known additives.
What we claim is:
1. A compound represented by the following formula:
RIO
wherein M is a calcium, barium, nickel, cadmium, lead or zinc atom; and R, R, R" and R' are alkyl radicals containing up to 10 carbons, at least one of R, R, R" and R having the formula:
2. A compound as claimed in claim 1 wherein said hydroxy group is sterically hindered by vicinally positioned secondary or tertiary alkyl groups.
3. A compound as claimed in claim 1 wherein said hydroxy group is in the para position sterically hindered by vicinally positioned tertiary butyl groups.
4. A compound as claimed in claim 1 having the name bis[( 3,5 di-tert.butyl-4-hydroxy-benzy1)propyl] zinc dithiophosphate.
5. A compound as claimed in claim 1 having the name (4 methyl -2- pentyl) [(3,S-di-tert.butyl-4-hydroxy-benzyl)-propyl] zinc dithiophosphate.
6. A compound as claimed in claim 1 having the name cetyl[(3,5 di tert.buty1-4-hydroxy-benzyl)-propyl] zinc dithiophosphate.
References Cited UNITED STATES PATENTS Rutherford et al. 25235 Cook et a1 260448 X Reifi et a1. 25232.7 Welsh 25232.7 Arakelian 260429.9 Miller 260429.9 Goldsmith 260429.9 X
TOBIAS E. LEVOW, Primary Examiner H. M. S. S NEED, Assistant Examiner US Cl. X.R.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2358267 | 1967-12-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3654329A true US3654329A (en) | 1972-04-04 |
Family
ID=11208305
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US780906A Expired - Lifetime US3654329A (en) | 1967-12-06 | 1968-12-03 | Zinc dithiophosphates |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3654329A (en) |
| AT (1) | AT291291B (en) |
| BE (1) | BE724936A (en) |
| CH (1) | CH505886A (en) |
| FR (1) | FR1594153A (en) |
| GB (1) | GB1204798A (en) |
| NL (1) | NL6817504A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2636583A1 (en) * | 1975-08-15 | 1977-02-24 | Mobil Oil Corp | LUBRICANT COMPOSITION |
| US4226733A (en) * | 1978-11-17 | 1980-10-07 | Mobil Oil Corporation | Lubricant compositions stabilized against ultra-violet degradation |
| US5013465A (en) * | 1987-12-23 | 1991-05-07 | Exxon Chemical Patents, Inc. | Dithiophosphates |
| CN110563760A (en) * | 2019-10-16 | 2019-12-13 | 宜春学院 | Preparation method of thiophosphate compound |
-
1968
- 1968-11-04 GB GB52236/68A patent/GB1204798A/en not_active Expired
- 1968-12-03 US US780906A patent/US3654329A/en not_active Expired - Lifetime
- 1968-12-04 CH CH1814368A patent/CH505886A/en not_active IP Right Cessation
- 1968-12-05 BE BE724936D patent/BE724936A/xx not_active IP Right Cessation
- 1968-12-06 NL NL6817504A patent/NL6817504A/xx unknown
- 1968-12-06 FR FR1594153D patent/FR1594153A/fr not_active Expired
- 1968-12-06 AT AT1193768A patent/AT291291B/en not_active IP Right Cessation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2636583A1 (en) * | 1975-08-15 | 1977-02-24 | Mobil Oil Corp | LUBRICANT COMPOSITION |
| US4226733A (en) * | 1978-11-17 | 1980-10-07 | Mobil Oil Corporation | Lubricant compositions stabilized against ultra-violet degradation |
| US5013465A (en) * | 1987-12-23 | 1991-05-07 | Exxon Chemical Patents, Inc. | Dithiophosphates |
| CN110563760A (en) * | 2019-10-16 | 2019-12-13 | 宜春学院 | Preparation method of thiophosphate compound |
Also Published As
| Publication number | Publication date |
|---|---|
| NL6817504A (en) | 1969-06-10 |
| CH505886A (en) | 1971-04-15 |
| GB1204798A (en) | 1970-09-09 |
| FR1594153A (en) | 1970-06-01 |
| BE724936A (en) | 1969-05-16 |
| AT291291B (en) | 1971-07-12 |
| DE1808492A1 (en) | 1969-06-19 |
| DE1808492B2 (en) | 1976-12-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3654155A (en) | Esters of phosphorodithioates | |
| US2443264A (en) | Compounded lubricating oil | |
| US2565920A (en) | Triesters of dithiophosphoric acid | |
| US2736737A (en) | Phosphate partial ester-aldehyde condensation product and lubricant containing the same | |
| US2734088A (en) | Monomeric condensation products of | |
| US2813830A (en) | Hydrocarbon oil compositions | |
| US3277133A (en) | Phosphorus-, sulfur-, and metal-containing composition | |
| US2589326A (en) | Organic phosphorus ester-p2s5 reaction products and oil compositions containing the same | |
| US3567638A (en) | Novel phosphorus-containing adducts in oil compositions containing the same | |
| US3350348A (en) | Lubricating oil additives | |
| US2365938A (en) | Wax substituted diaryl dithiophosphoric acids and salts thereof | |
| US2488134A (en) | Sulfur-containing aromatic compounds | |
| US2783204A (en) | Corrosion preventing agent | |
| US3654329A (en) | Zinc dithiophosphates | |
| US2619508A (en) | Polyether-alcohols containing thioether side chains | |
| US3089850A (en) | Phosphorothiolothionates derived from glycols | |
| GB1583690A (en) | Thio-compounds derivable from epichlorohydrin and their use as lubricant additives | |
| US4113634A (en) | Metal aryl dithiophosphates and their manufacture | |
| US2596141A (en) | Monoalkyl diphenyl phosphate esters | |
| US2472517A (en) | Addition agents for mineral oil lubricants | |
| DE3854250T2 (en) | Lubricating oil additives containing borate derivatives of mixed nonaryldiolphosphorodithioates. | |
| US2713557A (en) | Basic phenates to inhibit silver corrosion in thiophosphate-containing lubricating oils | |
| US3595792A (en) | Lubricating oil additives | |
| US3929653A (en) | Lubricant additives | |
| US5132031A (en) | Copper dihydrocarbyl dithiophosphyl dithiophosphates, their preparation and their use as additives for lubricants |