US3045037A - Process for making phosphorus ester lube oil additive - Google Patents
Process for making phosphorus ester lube oil additive Download PDFInfo
- Publication number
- US3045037A US3045037A US65598A US6559860A US3045037A US 3045037 A US3045037 A US 3045037A US 65598 A US65598 A US 65598A US 6559860 A US6559860 A US 6559860A US 3045037 A US3045037 A US 3045037A
- Authority
- US
- United States
- Prior art keywords
- alkyl
- acid
- alcohol
- dithiophosphoric acid
- dithiophosphoric
- 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
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- 229910052698 phosphorus Inorganic materials 0.000 title description 18
- -1 phosphorus ester Chemical class 0.000 title description 18
- 239000000654 additive Substances 0.000 title description 15
- 239000011574 phosphorus Substances 0.000 title description 13
- 238000000034 method Methods 0.000 title description 12
- 230000000996 additive effect Effects 0.000 title description 10
- 239000010687 lubricating oil Substances 0.000 title description 8
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000002253 acid Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 11
- 125000002877 alkyl aryl group Chemical group 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 10
- 235000007586 terpenes Nutrition 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000003505 terpenes Chemical class 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003599 detergent Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 241000779819 Syncarpia glomulifera Species 0.000 description 5
- 230000003064 anti-oxidating effect Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000686 essence Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000001739 pinus spp. Substances 0.000 description 5
- 229940036248 turpentine Drugs 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005809 transesterification reaction Methods 0.000 description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical class OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical class CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical class CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical class OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 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
- 150000001712 car-3-ene derivatives Chemical class 0.000 description 1
- 229930007796 carene Natural products 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 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
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000010688 mineral lubricating oil Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 150000003017 phosphorus Chemical class 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
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003582 thiophosphoric acids Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C10M137/105—Thio derivatives not containing metal
-
- 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
- C07F9/18—Esters of thiophosphoric acids with hydroxyaryl 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
- 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
- C10M2223/047—Thioderivatives not containing metallic elements
Definitions
- the present invention relates more particularly to those additives that exercise an anti-oxidation, anti-corrosive and detergent action.
- the addition of anti-oxidation agents to the lubricants serves to prevent the formation during use, of oxidation products which are of an acid nature and therefore corrosive, and of resinous compounds more or less polymerised, and more or less soluble in oil, which give rise to oil-dregs or coatings adhering to the metal surfaces.
- the anti-oxidants of this type in use are generally various types of organic sulphur compounds, complex amines and other complex alkyl-aryl derivatives containing-two or three of the following elements: Cl, P, S, N, etc. These anti-oxidants for lubricants "are effective under heat.
- the anti-corrosives serve in a special manner to reduce corrosion of the points due to acid products of the oxidation of the engine lubricants. They are therefore fellowworkerswith the anti-oxidation agents and it is reckoned that their effect becomes apparent through the action of the corrosive products with which they co-operate in the formation of a protective layer on the metal surfaces of the moving working parts.
- the recognised anti-corrosives are composed chiefly of organic thioderivatives of phosphorus, arsenic, antimony, bismuth, and certain sulphur olefines, etc. i
- Detergents are employed in the preparation of modern lubricants for engines. They serve to avoid, in high temperature engines especially, the formation of gums which render liners sticky and glued, the'deposits of oil-dregs which end up by closing filters and oil piping, the formation of scaling which impairs the cooling of the pistons.
- Recognised detergents in general are composed of organic thiophosphates of Ba and Ca, of sulphur olefines and the corresponding alkaline earth soaps, of metal alkylthiophenolates, etc.
- One aim of the present invention is to produce an additive for lubricating'oils of the type of the organic derivatives of a thiophosphoric acid, possessing at the same time anti-oxidation and anti-corrosive characteristics, and, in addition, exercising a detergent action and giving to the lubricating oil a characteristic of preventing wear; these qualities making it particularly suitable to the modern engines with an Otto cycle (4-stroke engine working cycle) with a high compression ratio.
- Another aim of the present invention is to produce an additive of such a nature that it can be mixed with the" normal dispersing elements for lubricating oils such as oil-soluble polyvalent metal salts of petroleum sulphuric acids or of sulphur alkyl phenols, in order to preparev lubricants suitable for the most diverserequirements, and which will bes'table, easily kept in good condition, and which, when dissolved in mineral lubricating oil will not show a tendency to develop sulphuretted hydrogen in normal working conditions of the present day internal combustion engines.
- lubricating oils such as oil-soluble polyvalent metal salts of petroleum sulphuric acids or of sulphur alkyl phenols
- a still further object of the present invention is to make practicable a process of manufacturing such an additive for lubricating oils.
- the additive for lubricatingoils belonging to the group of thioderiv-atives of phosphorus, is characterised by the fact that it is a mixedneutral ester of dithiophosphoric acid and by the fact that the three groups which esterify the dithiophosphoric 'acid' are dilferent from 'each other and belong to diverse chemical groups, the first being an aliphatic radical, the second being an aromatic radical and the thirdbeing an alicyclic radical, these radicals being all linked directly to the phosphorus atom by means of atoms of O and S.
- the process for the production of the mixed neutral esters of dithiophosphoric acid according to the invention is characterised by the fact that it consists in preparing, in the first stage, an alkyl alkyl-aryl dithiophosphoric acid, and, in the second stage, in reacting by means of heat the alkyl alkyl-aryl dithiophosphoric acid thus obtained with an unsaturated monocyclic or bicyclic terpene.
- the alkyl alkyl-aryl dithiophosphoric acid is prepared by heating two molecules of an aliphatic alcohol and two molecules of an alkylphenol with pentasulphide of ence of a suitable solvent.
- the dithiophosphoric alkyl alkyl-aryl acid is prepared by heating four molecules of an aliphatic alcohol with pentasulphide of phosphorus until the corresponding dithiophosphoric dialkyl acid is formed; subsequently its transesterification is carried out by adding two molecules of alkylphenol, heating and driving off by distillation the alcohol corresponding to the substituted'radical.
- R primary secondary or tertiary alkyl radical, preferably with 2-12 atoms of carbon
- R the alkyl-aryl radical, in which the aryl radical is preferably a benzene one and'the alkyl radicals are formed by one or more chains of primary, secondary or carbon.
- I R" the cycloaliphatic radical of terpene'typel A tertiary hydrocarbons, preferably with 2-12 atoms of phosphorus in the pres
- the three radicals are not only different from each other but they belong to different classes of compounds and, to speak exactly, there are present contemporaneously aliphatic, alicyclic and aromatic radicals, all linked directly to the atom of P by atoms of O and S. In this way, the characteristics of the aliphatic, alicyclic and aromatic derivatives containing P and S are summed up in a single individual chemical unit.
- alkyl alkyl-aryl dithiophosphoric acids preferred are those in which both the esterifying alkyl radical and the one linked to the aromatic nucleus contain 2-l2 atoms of carbon.
- the alkyl alkyl-aryl alcohols employed in the preparation are, in general, ethyl, n-propyl, isopropyl alcohols, all the butyl, amyl, hexyl and heptyl alcohols, various alcohols with 8-12 atoms of carbon obtained by reduction of the corresponding fat acids, and primary ramified hydroxy-alcohols derived from propylene and butylene dimers.
- the alkylphenols are, on the other hand, characterised by an aryl group corresponding to a benzene nucleus, while the alkyl groups, which may be present to the number of one or more, are formed by chains of hydrocarbons with preferably 2-12 atoms of carbon.
- the most representative alkylphenols are the various isomeric isopropyland p-tert-butyl-phenols the octyl, nonyl and dodecyl phenols, and the corresponding higher homologues, that is, those products obtained in most cases of alkylation with olefines of the corresponding hydrocarbons.
- the bicyclic derivatives are to be preferred, as they ofier a better capacity to react with the dithiophosphoric acid esters.
- these derivatives the most important are, with the exception of monocyclodipentene, the various isomeric pinenes, the carenes, and the mixtures of natural origin which contain them in various degrees, such as the essences of turpentine from various sources (French, Greek, Portuguese, Spanish, German, American).
- the alcohol used is a secondary lower alcohol
- the alkylphenol has a lateral chain not very long and variously ramified
- the terpene is a pinene contained in turpentine essence.
- the preparation which leads to the formation of the final neutral ester is of the type of reactions of addition and is conducted first of all by preparing the alkyl alkylaryl dithiophosphoric acid, and next in order, by bringing such acid into contact with a monoor bicyclic unsaturated terpene and heating.
- the alkyl alkyl-aryl dithiophosphoric acid can be prepared by heating two molecules of one alcohol and two molecules of an alkylphenol with pentasulphide of phosphorus, preferably in the presence of a suitable solvent.
- the alkyl alkyl-aryl dithiophosphoric acid can be prepared by heating four molecules of an alcohol with pentasulphide of phosphorus up to the formation of the corresponding dialkyl dithiophosphoric acid; the subsequent transesterification is carried out by adding two molecules of an alkylphenol, heating and eliminating by distillation the alcohol corresponding to the substituted radical.
- the alcohol which, especially if a primary one, has a very great reaction afiinity with the pentasulphide of phosphorus, is the first to react by forming a certain amount of the corresponding dialkyl dithiophosphoric acid. This subsequently reacts by transesterification with the alkylphenol giving rise to alkyl alkyl-aryl dithiophosphoric acid; a molecule of alcohol is freed which in its turn combines further with the pentasulphide of phosphorus, thus renewing the cycle.
- dialkyl dithiophosphoric acids are notably unstable at high temperatures, and on the other hand it has been observed that the instability is lower in the case of alkyl alkyl-aryl dithiophosphoric acids
- the reaction is at first carried out at a temperature not too high and later the temperature is raised to reach the boiling temperature of the solution (112-115 C.) (or close to it, according to the concentration) and kept at this value until the P 5 is completely dissolved. Both stages of the reaction are conducted in an atmosphere of nitrogen. The final solution is filtered and, by working at a maximum temperature of C. and under a vacuum lower than 20 mm., the solvent is almost entirely eliminated. If this method is followed, products with uniform characteristics and an adequate degree of purity can be obtained with good yields.
- the first phase of the reaction is represented by the formation of dialkyl dithiophosphoric acid by a stoichiometric reaction of an alcohol with P 8
- the reaction is carried out according to the usual procedure characteristic of this kind of preparation.
- the reaction temperature according to the type of alcohol, varies between 70 and 95 C.
- the calculated amount of alkylphenol is added into the same reaction vessel.
- the temperature is raised to C. and the alcohol formed in the transesterification is distilled until the required stoichiometric amount is obtained.
- the reacting mass becomes more and more viscous, it is difficult to obtain an effective stirring of the mixture and phenomena of local overheating occur.
- the first process which, permits, above all, working at lower temperatures and therefore reduces to a minimum the decomposition and oxidation phenomena characteristic of the dithiophosphoric esters.
- the reaction of addition between this acid and an unsaturated terpene is then always carried out with an excess of terpene, which, as required, varies from 5 to 40%.
- This reaction is slightly exothermic, and it is convenient to add the terpene or the acid (according to which is considered more convenient) in successive small lots, taking care that the temperature does not exceed 35-40 C.
- Heating at 110-120 C. is then prolonged for 1-5 hours, according to the reacting substances; practically neutral products are thus obtained which, after further washing with a solution of 5% Na CO and with H 0, and evaporation of the excess terpene at 100 C. under a vacuum of 2050 mm., are ready for practical use.
- Example 1 2-ethylhexyl-octylphenyl-dithiophosphoric acid is prepared by dissolving in the cold 250 g. of octylphenol and 158 g. of 2-ethylhexyl alcohol in 900 ml. of toluene; to the solution thus obtained is added, as rapidly as possible, 135 g. of pentasulphide of phosphorus, the temperature being kept at or below 40 C. Nitrogen is then introduced on to the surface in order to exclude any contact with air. The mixture is heated with stirring at 95 C. for one hour, the temperature is increased to 115 C. and the heating is prolonged until complete homogeneity of the mass is obtained. It is cooled at approximately 30 C.
- Example 2 Iso-propyl-octylphenyl-dithiophosphoric acid is prepared by dissolving in the cold 600 g. of octylphenyl and 176 g. of isopropyl alcohol in 70 ml. of toluene. 324 g. of pentasulphide is rapidly added, the temperature being kept at or below 40 C. Nitrogen is introduced superficially and the mixture is heated while being agitated for 1 hour at 80 C., and afterwards at 115 C. until complete homogeneity of the load is obtained. It is cooled at approximately 30 C., filtered and the solvent is evaporated from the filtrate at first under a vacuum of 100-200 mm. with a temperature rising from 60 to 100 C., finally at 100 C. and 20 mm. up to the complete elimination of the solvent. 1109 g. are obtained of a product which, on
- the I yield is 1026 g. of 100% iso-propyl-octyl-phenyl-dithio-V phosphoric acid.
- n-Butyl-nonylphenyl-dithiophosphoric acid is prepared by dissolving in the cold 446 g. of nonylphenol and 150 g. of n-butanol in 1000 ml. of toluene, adding rapidly 25 g. of pentasulphide of phosphorus and heating the mixture at 110-115 C. up to complete homogeneity. It is allowed to cool, is filtered and from the filtrate the solvent is removed completely by evaporating at first under a vacuum of 150-180 mm. and re-heating gradually from 60 to 100 C., finally'under a vacuum of 20 mm. at
- Example 4 phenol are added to the product, without cooling.
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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)
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Description
United States Patent fifice 3,045,037 Patented Jlily 1:7, 19.62
' 3,045,037 PROCESS FOR MAKING PHOSPHORUS ESTER LUBE OIL ADDITIVE Luigi Benedetti, Corso Sempione 33, Milan, Italy No Drawing. Filed Oct. 28, 1960, Ser. No. 65,598 Claims priority, application Italy Nov. 7, 1959 1 Claim. (Cl. 260-461) and the formation of coatings and deposits on the engine parts. Among the more important lubricant additives may be noted anti-oxidation, anti-corrosion, anti-rust, anti-foam additives, thickening agents, additives to'improve the viscosity index, lubricity agents and detergents. Each type of additive gives rise to its own particular effect and so it is obvious that lubricating oils require the addition of suitable mixtures of such additives according to the characteristic features such oils must have.
The present invention relates more particularly to those additives that exercise an anti-oxidation, anti-corrosive and detergent action. The addition of anti-oxidation agents to the lubricants serves to prevent the formation during use, of oxidation products which are of an acid nature and therefore corrosive, and of resinous compounds more or less polymerised, and more or less soluble in oil, which give rise to oil-dregs or coatings adhering to the metal surfaces. The anti-oxidants of this type in use are generally various types of organic sulphur compounds, complex amines and other complex alkyl-aryl derivatives containing-two or three of the following elements: Cl, P, S, N, etc. These anti-oxidants for lubricants "are effective under heat.
The anti-corrosives serve in a special manner to reduce corrosion of the points due to acid products of the oxidation of the engine lubricants. They are therefore fellowworkerswith the anti-oxidation agents and it is reckoned that their effect becomes apparent through the action of the corrosive products with which they co-operate in the formation of a protective layer on the metal surfaces of the moving working parts. The recognised anti-corrosives are composed chiefly of organic thioderivatives of phosphorus, arsenic, antimony, bismuth, and certain sulphur olefines, etc. i
Detergents are employed in the preparation of modern lubricants for engines. They serve to avoid, in high temperature engines especially, the formation of gums which render liners sticky and glued, the'deposits of oil-dregs which end up by closing filters and oil piping, the formation of scaling which impairs the cooling of the pistons. Recognised detergents in general are composed of organic thiophosphates of Ba and Ca, of sulphur olefines and the corresponding alkaline earth soaps, of metal alkylthiophenolates, etc.
From all the above it is evident that in the three kinds of additive mentioned, the organic derivatives of thiophosphoric acid or organic thiophosphates are frequently used. One aim of the present invention is to produce an additive for lubricating'oils of the type of the organic derivatives of a thiophosphoric acid, possessing at the same time anti-oxidation and anti-corrosive characteristics, and, in addition, exercising a detergent action and giving to the lubricating oil a characteristic of preventing wear; these qualities making it particularly suitable to the modern engines with an Otto cycle (4-stroke engine working cycle) with a high compression ratio.
Another aim of the present invention is to produce an additive of such a nature that it can be mixed with the" normal dispersing elements for lubricating oils such as oil-soluble polyvalent metal salts of petroleum sulphuric acids or of sulphur alkyl phenols, in order to preparev lubricants suitable for the most diverserequirements, and which will bes'table, easily kept in good condition, and which, when dissolved in mineral lubricating oil will not show a tendency to develop sulphuretted hydrogen in normal working conditions of the present day internal combustion engines.
A still further object of the present invention is to make practicable a process of manufacturing such an additive for lubricating oils.
In more particular detail, the additive for lubricatingoils, according to the invention belonging to the group of thioderiv-atives of phosphorus, is characterised by the fact that it is a mixedneutral ester of dithiophosphoric acid and by the fact that the three groups which esterify the dithiophosphoric 'acid' are dilferent from 'each other and belong to diverse chemical groups, the first being an aliphatic radical, the second being an aromatic radical and the thirdbeing an alicyclic radical, these radicals being all linked directly to the phosphorus atom by means of atoms of O and S.
The process for the production of the mixed neutral esters of dithiophosphoric acid according to the invention is characterised by the fact that it consists in preparing, in the first stage, an alkyl alkyl-aryl dithiophosphoric acid, and, in the second stage, in reacting by means of heat the alkyl alkyl-aryl dithiophosphoric acid thus obtained with an unsaturated monocyclic or bicyclic terpene. According to a characteristic of the invention, the alkyl alkyl-aryl dithiophosphoric acid is prepared by heating two molecules of an aliphatic alcohol and two molecules of an alkylphenol with pentasulphide of ence of a suitable solvent.
According to another characteristic of the invention the dithiophosphoric alkyl alkyl-aryl acid is prepared by heating four molecules of an aliphatic alcohol with pentasulphide of phosphorus until the corresponding dithiophosphoric dialkyl acid is formed; subsequently its transesterification is carried out by adding two molecules of alkylphenol, heating and driving off by distillation the alcohol corresponding to the substituted'radical.
From all the above it is evident that the mixed neutral ester of dithiophosphoric acid according to the invention, derives from the dithiophosphoric acid which has the following structural formula:
HO HO P=S HS in which the hydrogen atoms are replaced by three different radicals indicated respectively by R, R" and R'" I R'o R"0P=s V RI/IS where R=primary secondary or tertiary alkyl radical, preferably with 2-12 atoms of carbon, R=the alkyl-aryl radical, in which the aryl radical is preferably a benzene one and'the alkyl radicals are formed by one or more chains of primary, secondary or carbon. I R"=the cycloaliphatic radical of terpene'typel A tertiary hydrocarbons, preferably with 2-12 atoms of phosphorus in the pres As is apparent, the three radicals are not only different from each other but they belong to different classes of compounds and, to speak exactly, there are present contemporaneously aliphatic, alicyclic and aromatic radicals, all linked directly to the atom of P by atoms of O and S. In this way, the characteristics of the aliphatic, alicyclic and aromatic derivatives containing P and S are summed up in a single individual chemical unit.
The alkyl alkyl-aryl dithiophosphoric acids preferred are those in which both the esterifying alkyl radical and the one linked to the aromatic nucleus contain 2-l2 atoms of carbon. The alkyl alkyl-aryl alcohols employed in the preparation are, in general, ethyl, n-propyl, isopropyl alcohols, all the butyl, amyl, hexyl and heptyl alcohols, various alcohols with 8-12 atoms of carbon obtained by reduction of the corresponding fat acids, and primary ramified hydroxy-alcohols derived from propylene and butylene dimers.
The alkylphenols are, on the other hand, characterised by an aryl group corresponding to a benzene nucleus, while the alkyl groups, which may be present to the number of one or more, are formed by chains of hydrocarbons with preferably 2-12 atoms of carbon. The most representative alkylphenols are the various isomeric isopropyland p-tert-butyl-phenols the octyl, nonyl and dodecyl phenols, and the corresponding higher homologues, that is, those products obtained in most cases of alkylation with olefines of the corresponding hydrocarbons.
Among the unsaturated terpenes, the bicyclic derivatives, in particular, are to be preferred, as they ofier a better capacity to react with the dithiophosphoric acid esters. Among these derivatives, the most important are, with the exception of monocyclodipentene, the various isomeric pinenes, the carenes, and the mixtures of natural origin which contain them in various degrees, such as the essences of turpentine from various sources (French, Greek, Portuguese, Spanish, German, American).
Those compounds are preferred especially in which the alcohol used is a secondary lower alcohol, the alkylphenol has a lateral chain not very long and variously ramified, and the terpene is a pinene contained in turpentine essence. When these requirements are met, a product soluble in oil is obtained, which otfers, in comparison with other compounds of the series, a greater anti-corrosive activity and anti-oxidation property, due to the higher content of phosphorus and sulphur.
The preparation which leads to the formation of the final neutral ester is of the type of reactions of addition and is conducted first of all by preparing the alkyl alkylaryl dithiophosphoric acid, and next in order, by bringing such acid into contact with a monoor bicyclic unsaturated terpene and heating.
As regards the preparation of the alkyl alkyl-aryl dithiophosphoric acid, it can be accomplished, as already said, in the following manner:
(1) The alkyl alkyl-aryl dithiophosphoric acid can be prepared by heating two molecules of one alcohol and two molecules of an alkylphenol with pentasulphide of phosphorus, preferably in the presence of a suitable solvent.
(2) The alkyl alkyl-aryl dithiophosphoric acid can be prepared by heating four molecules of an alcohol with pentasulphide of phosphorus up to the formation of the corresponding dialkyl dithiophosphoric acid; the subsequent transesterification is carried out by adding two molecules of an alkylphenol, heating and eliminating by distillation the alcohol corresponding to the substituted radical.
If the first process is used, during the heating of the alcohol, the pentasulphide of phosphorus and of the alkylphenol, the alcohol, which, especially if a primary one, has a very great reaction afiinity with the pentasulphide of phosphorus, is the first to react by forming a certain amount of the corresponding dialkyl dithiophosphoric acid. This subsequently reacts by transesterification with the alkylphenol giving rise to alkyl alkyl-aryl dithiophosphoric acid; a molecule of alcohol is freed which in its turn combines further with the pentasulphide of phosphorus, thus renewing the cycle. For this reason, since dialkyl dithiophosphoric acids are notably unstable at high temperatures, and on the other hand it has been observed that the instability is lower in the case of alkyl alkyl-aryl dithiophosphoric acids, the reaction is at first carried out at a temperature not too high and later the temperature is raised to reach the boiling temperature of the solution (112-115 C.) (or close to it, according to the concentration) and kept at this value until the P 5 is completely dissolved. Both stages of the reaction are conducted in an atmosphere of nitrogen. The final solution is filtered and, by working at a maximum temperature of C. and under a vacuum lower than 20 mm., the solvent is almost entirely eliminated. If this method is followed, products with uniform characteristics and an adequate degree of purity can be obtained with good yields.
Should the reaction be carried out from the beginning at a temperature of 1l2115 C., the characteristics of the product, particularly in respect of purity, tend to worsen or deteriorate.
If the second process is employed, the first phase of the reaction is represented by the formation of dialkyl dithiophosphoric acid by a stoichiometric reaction of an alcohol with P 8 The reaction is carried out according to the usual procedure characteristic of this kind of preparation. The reaction temperature, according to the type of alcohol, varies between 70 and 95 C. Into the same reaction vessel, Without any particular precautionary measures and immediately after the P 5 has been completely dissolved, the calculated amount of alkylphenol is added. Thereafter the temperature is raised to C. and the alcohol formed in the transesterification is distilled until the required stoichiometric amount is obtained. During this operation, as the reacting mass becomes more and more viscous, it is difficult to obtain an effective stirring of the mixture and phenomena of local overheating occur.
All these operations are carried out in a nitrogen atmosphere. The products thus obtained, although they possess, with satisfactory uniformity, the chemical and physical characteristics of the products obtained by the first process, are characterised by a lesser degree of purity and by a notably higher tendency to deterioration. The yields are slightly lower than those obtained by the first process.
It is therefore preferable, in most cases, to use the first process which, permits, above all, working at lower temperatures and therefore reduces to a minimum the decomposition and oxidation phenomena characteristic of the dithiophosphoric esters.
Once the alkyl alkyl-aryl dithiophosphoric acid has been prepared according to one of the two processes, the reaction of addition between this acid and an unsaturated terpene is then always carried out with an excess of terpene, which, as required, varies from 5 to 40%. This reaction is slightly exothermic, and it is convenient to add the terpene or the acid (according to which is considered more convenient) in successive small lots, taking care that the temperature does not exceed 35-40 C. Heating at 110-120 C. is then prolonged for 1-5 hours, according to the reacting substances; practically neutral products are thus obtained which, after further washing with a solution of 5% Na CO and with H 0, and evaporation of the excess terpene at 100 C. under a vacuum of 2050 mm., are ready for practical use.
The anti-oxidation, anti-corrosive and detergent properties of the products of the present invention were tested on a W1 Petter Laboratory engine. The results obtained consistently showed the high anti-corrosive and anti- Hereunder are given some examples of the preparation of the mixed neutral esters of dithiophosphoric acid according to the invention.
Example 1 (a) 2-ethylhexyl-octylphenyl-dithiophosphoric acid is prepared by dissolving in the cold 250 g. of octylphenol and 158 g. of 2-ethylhexyl alcohol in 900 ml. of toluene; to the solution thus obtained is added, as rapidly as possible, 135 g. of pentasulphide of phosphorus, the temperature being kept at or below 40 C. Nitrogen is then introduced on to the surface in order to exclude any contact with air. The mixture is heated with stirring at 95 C. for one hour, the temperature is increased to 115 C. and the heating is prolonged until complete homogeneity of the mass is obtained. It is cooled at approximately 30 C. and is filtered. The filtrate is evaporated under a vacuum of 100-150 mm. at a heating temperature gradually increasing from 60 to 100 C. .until the solvent is completely eliminated. 345 g. of product is obtained, which after titration with a solution of 0.1 N alcoholic potash in the presence of phenolphthalein, or else with an excess of 0.1 iodine, shows an average equivalent weight of 454. The yield therefore is 335.5 g. of 100% product.
(b) To the charge obtained by the previous preparation are added 144 g. of Portuguese turpentine essence, care being taken that the temperature does not go beyond 40 C It is heated and stirred at 150 for 2 hours. It is allowed to cool at 100 C. and the excess of turpentine essence is evaporated at 100 and under a vacuum of 20 mm. 426 g. of Z-ethylhexyl-ethylphenyl-bornyl-dithiophosphate is obtained which can be used as an additive.
On analysis, a sample contained 5.44% P, 9.97% S.
Example 2 (a) Iso-propyl-octylphenyl-dithiophosphoric acid is prepared by dissolving in the cold 600 g. of octylphenyl and 176 g. of isopropyl alcohol in 70 ml. of toluene. 324 g. of pentasulphide is rapidly added, the temperature being kept at or below 40 C. Nitrogen is introduced superficially and the mixture is heated while being agitated for 1 hour at 80 C., and afterwards at 115 C. until complete homogeneity of the load is obtained. It is cooled at approximately 30 C., filtered and the solvent is evaporated from the filtrate at first under a vacuum of 100-200 mm. with a temperature rising from 60 to 100 C., finally at 100 C. and 20 mm. up to the complete elimination of the solvent. 1109 g. are obtained of a product which, on
analysis, gives an average equivalent weight of 385. The I yield is 1026 g. of 100% iso-propyl-octyl-phenyl-dithio-V phosphoric acid.
(b) To the load obtained by the previous reaction are added 450 g. of essence of Greek turpentine, carebeing taken not to go beyond C.; thereafter it is heated for 3 hours at 150" c., and allowed to cool at 100 1276 g. of product are obtained which can be used directly as an additive. The
and under a vacuum of 20 mm.
analysis of a sample gave the following results: 6.61% P and 11.6% S.
- Example 3 n-Butyl-nonylphenyl-dithiophosphoric acid is prepared by dissolving in the cold 446 g. of nonylphenol and 150 g. of n-butanol in 1000 ml. of toluene, adding rapidly 25 g. of pentasulphide of phosphorus and heating the mixture at 110-115 C. up to complete homogeneity. It is allowed to cool, is filtered and from the filtrate the solvent is removed completely by evaporating at first under a vacuum of 150-180 mm. and re-heating gradually from 60 to 100 C., finally'under a vacuum of 20 mm. at
100 C. 738 g. of product are obtained with an average equivalent weight of 427. The yield is 671 g. of 100% n butyl-nonylphenol-dithiophosphoric acid. The product can be employed just as it is in condensations with terpenes.
Example 4 phenol are added to the product, without cooling. The
mixture thus obtained is stirred continuously and kept at 130 C. for half an hour.
' ing the temperature from 130 to 150 C., 250 ml. of methphoric acid suitable for use in the production of additives for lubricating oils belonging to mixed neutral esters of dithiophosphoric acid, comprisingthe steps ofheating four molecules of a saturated monohydric aliphatic alcohol with phosphorus pentasulfide to form the corresponding dialkyl-dithiophosphoric acid, and subsequently transesterifying by addition of two molecules of alkylphenol, heating and removal by distillation of the alcohol corresponding to the substituted radical.
References Cited in the file of this patent UNITED STATES PATENTS 2,506,310 Mikeska May 2, 1950 2,627,523 Hook et a1. Feb. 3, 1953 2,665,295 Augustine Jan. 5, 1954 2,689,258 McDermott Sept. 14, 1954 Thereafter, by gradually rais
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IT3045037X | 1959-11-07 |
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US65598A Expired - Lifetime US3045037A (en) | 1959-11-07 | 1960-10-28 | Process for making phosphorus ester lube oil additive |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3127349A (en) * | 1964-03-31 | Lubricating oil compositions having a | ||
US3190677A (en) * | 1964-04-08 | 1965-06-22 | Ralph C Robbins | Clevis with spring-operated pin |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2506310A (en) * | 1946-12-28 | 1950-05-02 | Standard Oil Dev Co | Lubricating oil composition |
US2627523A (en) * | 1950-08-30 | 1953-02-03 | American Cyanamid Co | S-(sulfurized terpene hydrocarbon) dithiophosphoric acid triesters and methods of producing the same |
US2665295A (en) * | 1947-10-28 | 1954-01-05 | Socony Vacuum Oil Co Inc | Diesters of dithiophosphoric acids and terpenes |
US2689258A (en) * | 1948-04-21 | 1954-09-14 | Standard Oil Dev Co | Reaction of terpenes with thiophosphorous acid esters and products thereof |
-
1960
- 1960-10-28 US US65598A patent/US3045037A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2506310A (en) * | 1946-12-28 | 1950-05-02 | Standard Oil Dev Co | Lubricating oil composition |
US2665295A (en) * | 1947-10-28 | 1954-01-05 | Socony Vacuum Oil Co Inc | Diesters of dithiophosphoric acids and terpenes |
US2689258A (en) * | 1948-04-21 | 1954-09-14 | Standard Oil Dev Co | Reaction of terpenes with thiophosphorous acid esters and products thereof |
US2627523A (en) * | 1950-08-30 | 1953-02-03 | American Cyanamid Co | S-(sulfurized terpene hydrocarbon) dithiophosphoric acid triesters and methods of producing the same |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3127349A (en) * | 1964-03-31 | Lubricating oil compositions having a | ||
US3190677A (en) * | 1964-04-08 | 1965-06-22 | Ralph C Robbins | Clevis with spring-operated pin |
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