US2488662A - Metal organo-phosphates - Google Patents
Metal organo-phosphates Download PDFInfo
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- US2488662A US2488662A US679262A US67926246A US2488662A US 2488662 A US2488662 A US 2488662A US 679262 A US679262 A US 679262A US 67926246 A US67926246 A US 67926246A US 2488662 A US2488662 A US 2488662A
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- Prior art keywords
- salts
- zinc
- acid
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- cadmium
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- 229910019142 PO4 Inorganic materials 0.000 title description 10
- 229910052751 metal Inorganic materials 0.000 title description 4
- 239000002184 metal Substances 0.000 title description 4
- 150000003839 salts Chemical class 0.000 description 31
- 239000002253 acid Substances 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 150000002148 esters Chemical class 0.000 description 18
- 239000011701 zinc Substances 0.000 description 18
- -1 hexadecenyl Chemical group 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 13
- 150000003254 radicals Chemical class 0.000 description 13
- 229910052725 zinc Inorganic materials 0.000 description 13
- 235000019441 ethanol Nutrition 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 10
- 235000021317 phosphate Nutrition 0.000 description 8
- 150000003751 zinc Chemical class 0.000 description 8
- 235000011007 phosphoric acid Nutrition 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 6
- RNPXCFINMKSQPQ-UHFFFAOYSA-N dicetyl hydrogen phosphate Chemical class CCCCCCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCCCCCC RNPXCFINMKSQPQ-UHFFFAOYSA-N 0.000 description 6
- 150000005690 diesters Chemical class 0.000 description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 150000001661 cadmium Chemical class 0.000 description 4
- 229910052793 cadmium Inorganic materials 0.000 description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OISMQLUZKQIKII-UHFFFAOYSA-L dichlorocadmium;hydrate Chemical compound O.[Cl-].[Cl-].[Cd+2] OISMQLUZKQIKII-UHFFFAOYSA-L 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- ZUVCYFMOHFTGDM-UHFFFAOYSA-N hexadecyl dihydrogen phosphate Chemical class CCCCCCCCCCCCCCCCOP(O)(O)=O ZUVCYFMOHFTGDM-UHFFFAOYSA-N 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- CUSOQKDDRMHSPY-UHFFFAOYSA-N pentyl phenyl hydrogen phosphate Chemical compound CCCCCOP(O)(=O)OC1=CC=CC=C1 CUSOQKDDRMHSPY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- KUPGJMJHAFGISS-UHFFFAOYSA-L zinc;hexadecyl phosphate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCOP([O-])([O-])=O KUPGJMJHAFGISS-UHFFFAOYSA-L 0.000 description 2
- MEEKGULDSDXFCN-UHFFFAOYSA-N 2-pentylphenol Chemical compound CCCCCC1=CC=CC=C1O MEEKGULDSDXFCN-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000218664 Gnetales Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000976924 Inca Species 0.000 description 1
- GRTSOKMSAFRDNI-UHFFFAOYSA-N P(=O)(O)(O)O.P(=O)(O)(O)O.P(=O)(O)(O)O.P(=O)(O)(O)O.P(=O)(O)(O)O.P(=O)(O)(O)O Chemical compound P(=O)(O)(O)O.P(=O)(O)(O)O.P(=O)(O)(O)O.P(=O)(O)(O)O.P(=O)(O)(O)O.P(=O)(O)(O)O GRTSOKMSAFRDNI-UHFFFAOYSA-N 0.000 description 1
- 235000006629 Prosopis spicigera Nutrition 0.000 description 1
- 240000000037 Prosopis spicigera Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000001204 arachidyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [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])* 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- OQPLDSDBGSRXSC-UHFFFAOYSA-N gnetal Natural products C1=CC(O)=CC=C1C1C(C=2C=C(O)C=C(O)C=2)C2=C(O)C=C(C=O)C=C2O1 OQPLDSDBGSRXSC-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 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
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 239000010688 mineral lubricating oil Substances 0.000 description 1
- 125000001421 myristyl 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])[H] 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
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 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 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- INJCIHHCTBEDST-UHFFFAOYSA-M potassium;dihexadecyl phosphate Chemical compound [K+].CCCCCCCCCCCCCCCCOP([O-])(=O)OCCCCCCCCCCCCCCCC INJCIHHCTBEDST-UHFFFAOYSA-M 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- YDTQNWNPMJTJCW-UHFFFAOYSA-L zinc;dihexadecyl phosphate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCOP([O-])(=O)OCCCCCCCCCCCCCCCC.CCCCCCCCCCCCCCCCOP([O-])(=O)OCCCCCCCCCCCCCCCC YDTQNWNPMJTJCW-UHFFFAOYSA-L 0.000 description 1
Images
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
- C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
- C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
-
- 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
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
-
- 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
-
- 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
- C10M2223/042—Metal salts thereof
-
- 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
Definitions
- ZGO -AZQL 1 2 s-in n o relates to hi h molecula we h wateninsom le,,mineral il-s u l inca d miuinsal s of acid esters-of ph sph r a d
- the polyvalent metal salts of acid esters, of phosphoric acid have value'asimprovement agents, 5 for mineral lubricating; oils.
- these polyyalentmetal. salts of acid-esters of phosphoric acid wil-l-be frequently- L ""2, Y oi, the invention to provide.
- polyvalent netalphosphatespd l'salts f acidfesters of Certain of thesepolyvalentmetal phosphates, phosp oric' "acid hIGIZLH IIB such-as the calciumand bariurnsalts, are waterwate r solii thaiilthealkalin earthfmetalsaltsfj solubleto a sufficient extent; or their solubilities of these ester'sandwhich aaiieieausas in mineral lubricating oils are sufficiently-40w; wear, (when used in mii leral, lubricating ils difiiculty is encountered in practice- Thus, I uoric 'ationxlasalf it isa common practice to disperse the polyvalent metal-phosphate in oil
- the radicals R1 and R2 contain each not less than 5 carbon atoms, preferably not less than carbon atoms, and preferably not more than carbon atoms. These radicals may be alkyl (e. g., amyl, hexyl, octyl, decyl, lauryl, tetradecyl, cetyl and eicosyl), alkylene (e.
- octenyl, hexadecenyl cycloaliphatic (e. g., napthenyl, cyclohexyl and methylcyclohexyl), aryl (e. g., phenyl), alkaryl (e. g., methylphenyl and cetyl phenyl), or aralkyl (e. g., benzyl, phenylstearyl and cetylbenzyl) radicals.
- Saturated aliphatic and cycloaliphatic radicals and aryl radicals substituted by one or more saturated aliphatic or cycloaliphatic radicals are preferred.
- Mixed radicals e. g., alkyl-cycloaliphatic and alkylalk-aryl
- mixed salts of monoand di-esters may be used, c. g., mixed zinc salts of mono-cetyl phosphoric acid and dicetyl phosphoric acid.
- the parent esters of the salts of the invention can be prepared by methods :well known in the art. Certain of the parent esters, e. g., monoand dicetyl phosphates and monoand dicholesteryl phosphates are described in the literature. Exemplary methods of preparation are provided by the specific examples below and by Plimmer and Burch, Journal of the Chemical Society, 1929, pages 279-291.
- the zinc and cadmium salts can be readily prepared from the parent esters, or from alkali metal salts of the same, by methods well known in the art, as exemplified by the specific examples and by Plimmer and Burch, op. cit.
- salts of the invention are: normal zinc and cadmium mono-amyl phophates, normal zinc ,and cadmium mono-octyl phosphates, normal zinc and cadmium mono-lauryl phosphates, normal zinc and cadmium mono-eicosyl phosphates, normal zinc and cadmium mono-methylcyclohexyl phosphates, normal zinc and cadmium mono-benzyl phosphates and normal zinc and cadmium mono-cetylphenyl phosphates; also, the corresponding normal zinc and cadmium di-amyl, di-octyl, di-lauryl, di-eicosyl, di-methylcyclohexyl, di-benzyl and dicetylphenyl phosphates.
- EXAMPLE 1 Monoand di-cetyl phosphoric acids and zinc and cadmium salts of the same A mixture of monoand dicetyl phosphoric acids was prepared by reacting 76 parts by weight of cetyl alcohol with a mixture of 17 parts of phosphorus pentoxide and 7 parts of pyrophosphoric acid at 270 F. The phosphorus pentoxide and pyrophosphoric acid were slowly added to the cetyl alcohol. The reaction was complete in two hours.
- the two acids were separated by dissolving in hot alcohol (to 20% concentration) and cooling to 40 F., causing precipitation of all the di-ester.
- the mono-ester was extracted from the alcoholic solution by means of aqueous KOH and the acid was freed by acidification with hydrochloric acid.
- the dicetyl phosphoric acid was recrystallized twice from ethyl alcohol and once from absolute alcohol. It had a melting point of 63-64.5 C. and analyzed 5.78% phosphorus (theory 5.6%).
- the monocetyl phosphoric acid analyzed 9.73% phosphorus (theory 9.64%).
- Both acids were white crystalline materials, the mono-ester having a flaky appearance and the diester, a granular appearance.
- the potassium salt was reacted with an equivalent amount of zinc chloride in alcohol solution at 150 F. over a period of 5 hours.
- the mixture was then cooled to precipitate white zinc monocetyl phosphate, which was washed with hot water to remove potassium chloride and unreacted zinc chloride, as shown by the appearance of only a faint cloud on treating cc. of filtrate with 10 cc. of 0.05 N silver nitrate.
- the salt was then washed with hot ethyl alcohol and dried in a desiccator at reduced pressure.
- dicetyl phosphoric acid was reacted with zinc oxide under reflux for 7 hours, in a solvent consisting of two parts by volume of benzene and one of ethyl a1- cohol.
- the desired salt was obtained as a solid precipitate and was washed with ethyl alcohol and extracted with hot benzene.
- the benzene was evaporated and the precipitated salt was dried under reduced pressure. Analysis: Found, per cent Zn, 5.9; per cent P, 5.4. Theory, per cent Zn, 5.6; per cent P, 5.4.
- Cadmium mono-cetyl phosphate was prepared and purified in the same manner as the corresponding zinc salt, cadmium chloride hydrate eing used in place of zinc chloride. Analysis: Found per cent Cd, 29.1; per cent P, 6.6. Theory, per cent Cd, 25.9; per cent P, 7.2.
- Cadmium dicetyl phosphate was prepared by reacting potassium dicetyl phosphate with an equivalent amount of cadmium chloride hydrate in alcohol at 150 F. The solid reaction product was washed with ethyl alcohol, dried, washed with hot benzene, recovered from benzene solution by evaporation of the solvent and dried under reduced pressure.
- EXAMPLE 2 Mono-tart. amylphenyl phosphoric acid and zinc and cadmium salts of the same p-Tert. amylphenol was reacted with an equivalent amount of phosphorus pentoxide at 300 F. for 3 hours.
- the reaction product was purified by recrystallization from petroleum ether to give white, flaky crystals, melting point 210-214 F.
- the zinc salt was prepared by refluxing one molecular proportion of the acid with 0.68 molecular proportion of zinc oxide in a solvent consisting of two parts by volume of benzene and one of ethyl alcohol for six hours.
- the solid reaction product was washed with 5% aqueous acetic acid to remove unreacted zinc oxide, then with ethyl alcohol to remove unreacted acid, and dried under reduced pressure.
- the cadmium salt was prepared by reacting the potassium salt of mono-p-tert. amylphenyl phosphoric acid with an equivalent amount of cadmium chloride hydrate at F. in ethyl alcohol.
- the solid reaction product which separated on cooling the mixture to room temperature was washed successively with water and ethyl alcohol to remove potassium chloride, and unreacted cadmium chloride and acid.
- salts of esters containing a total of at least 20 carbon atoms are freely oil-soluble, those containing less than this being more sparingly oilsoluble.
- a zinc salt of an acid ester of ortho phosphoric acid wherein each esterifying radical is a hydrocarbon group containing not less than 5 carbon atoms.
- a zinc salt of an acid ester of ortho phosphoric acid wherein each esterifying radical is a hydrocarbon group containing 5 to 20 carbon atoms, and said salt contains a total of not less than 10 carbon atoms.
- a zinc salt of an acid ester of ortho phosphoric acid wherein each esterifying radical is an alkyl hydrocarbon group containing 5 to 20 carbon atoms.
- each esterifying radical is a cycloaliphatic hydrocarbon group containing 5 to 20 carbon atoms.
- a zinc salt of an acid ester of ortho phosphoric acid wherein each esterifying radical is an alliaryl hydrocarbon group containing up to 20 carbon atoms.
- EXAMPLE 3 Zinc and cadmium dicyclohexyl phophates
- the parent acid ester is prepared by heating cyclohexanol with phosphorus pentoxide.
- the salts are prepared by precipitating them from an aqueous solution of the sodium or potassium salt of the parent acid, by addition of cadmium chloride or zinc acetate.
- EXAMPLE 4 Zinc and cadmium naphthenyl phosphates These are prepared by reacting naphthenyl alcohols (from reduction of naphthenic acids) with phosphorus pentoxide and precipitation of the desired salts from an aqueous solution of alkali metal salt of the parent acid ester by addition of cadmium chloride or zinc acetate.
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Description
Patented Nov. 22, 1949 2,488,662
METAL onoA go-rnosgggl rgs Bruce B. Farrington, James 0. .Glaytomand Johns, T. Rutherford, Berkeley, Qal i t}, ess ignors to California Beseaijch. (,3, l 1 ln S -F 1 1 l m n ia e svr ii i wai No Drawing. Application June. 25,1946
Serial No.-.6'79,2,62:.
7 Claims. Cl. ZGO -AZQL 1 2 s-in n o relates to hi h molecula we h wateninsom le,,mineral il-s u l inca d miuinsal s of acid esters-of ph sph r a d The polyvalent metal salts of acid esters, of phosphoric acid have value'asimprovement agents, 5 for mineral lubricating; oils. Thus, .theyare efiec; tiveywhen usednalone to increase the resistance phosphate to .obta-in the esire of suchioils-to oxidation andithey have particular u the l I efat value' nwhenusedilin combination. with ;a polyvalent =;metal..salt;of .an alkylphenol, to inhibitlO of it 'is required 1 corrosionof alloy ibearingslsuch as copperelead It ls anobje'ct of the present, inv,ention, to pro; bearings' Sewimwxampla Famngton et eee lee n va en gnetal's,tsbrai' United States Patent-., -No. 2,228,659 andcNeelyu h 5511; et al.,United States-PatentNo.x2,228,6'71.
For convenience, these polyyalentmetal. salts of acid-esters of phosphoric acid wil-l-be frequently- L ""2, Y oi, the invention ,to provide. referred; to as polyvalent netalphosphatespd l'salts f acidfesters of Certain of thesepolyvalentmetal phosphates, phosp oric' "acid hIGIZLH IIB such-as the calciumand bariurnsalts, are waterwate r solii thaiilthealkalin earthfmetalsaltsfj solubleto a sufficient extent; or their solubilities of these ester'sandwhich aaiieieausas in mineral lubricating oils are sufficiently-40w; wear, (when used in mii leral, lubricating ils difiiculty is encountered in practice- Thus, I uoric 'ationxlasalf it isa common practice to disperse the polyvalent metal-phosphate in oil in relativelylarge amount, of the orderof 50% on the weight of oil-phosphate solution, to produce a concentrate or stock solution; This concentrate is stored a'nd shipp ed to be blended with" more oil to produce a finished product containing about 0.25 to 2.0% of phosphate.- The aforesaid calcium andbarium phosphates are difiicult to blend homogeneously ,iPFQHS ch co Thes Land.,otherllobiectsofthe invention will centrates; d er na ished oi sc ntainiaa lesser be apparentfffio mthe ensu ng ,iscripiibnianeij; amounts are prone to form emulsions 0n agitation the 'apbended claims. with ,water, or they may ,fail to ,pass, stringent We-l'iaiefdisco ifed that thezincandeadmium acceptance, tests which, i clude centrituging, 9 15,35 salts of'acid esteem phosphoricacidai'e superior}; h p ed. 7 v in that they .are'characterif zedby lowlw ater-solll Certain,other polyv n metaL- Q p atessu h v, bility jand .hi h ToihsOIubilityQj Moreover; they dog as the alminum phosphates, although more. 011; not ca e xcessiy ,wear'lof workin lbafls of soluble and less water-soluble, cause, some .diffi: machine I .lilbricat'edlby mineral, oil s; oont i i'fl culty, owing to wear. of working-partsoi internal 40 them, combustion engines, such ascylinder andpiston, The salts of the inventionarelof two types, d walls and'piston rings. v rived from the mono estersian Jthe (ll-esters:
Theabove-mentioned oil-Water solubility difi'ie culties can be solvediby. employing phosphoric, /0,-R 1 O,R1., esters of sufiiciently high moleculanweight aloe-V :y o= ,p hols or,phenols,-but{to obviate. these difliculties 3 fully it is necessary, by this means, to .useesteri q fying-- radicals of excessively high .molecula 1 'ea eis weight. These excessively highumolecular weight-m Mono-esters radicals are more expensive than.the. more, com mon radicals of lowermolecular weight, contain 7. $-9 mqn -gstersma bei pormal salts ing 5 to 20 carbonatoms. Also, the ester ifying. I (Ml-511904) or acld salts QQ@=; radical functions primarily as-an oil-solubilizingf. In theabpyertormulaaRrandRz-arehydrocarbon t-4 t e e t ven b in }a ac a o h --.l e lsnwhic .m b subs it ted;l wereab e s h t i m arte brit a-zim e ei meta nshr r o s bs itueu..mnc M11 s n .l uszea eua sf .-ti e teatthe sa iainae a i salt .maye 59llq i i rmeqli ema either the monoor the ii-esters. Normal salts of the types R1 R1 o t t o=r M o=r '-o-M-o-i =o PM t ILA are preferred, and of these the salts of the diesters are preferred as being more oil-soluble. The radicals R1 and R2 contain each not less than 5 carbon atoms, preferably not less than carbon atoms, and preferably not more than carbon atoms. These radicals may be alkyl (e. g., amyl, hexyl, octyl, decyl, lauryl, tetradecyl, cetyl and eicosyl), alkylene (e. g., octenyl, hexadecenyl), cycloaliphatic (e. g., napthenyl, cyclohexyl and methylcyclohexyl), aryl (e. g., phenyl), alkaryl (e. g., methylphenyl and cetyl phenyl), or aralkyl (e. g., benzyl, phenylstearyl and cetylbenzyl) radicals. Saturated aliphatic and cycloaliphatic radicals and aryl radicals substituted by one or more saturated aliphatic or cycloaliphatic radicals are preferred.
Mixed radicals, e. g., alkyl-cycloaliphatic and alkylalk-aryl, may be used. Likewise, mixed salts of monoand di-esters may be used, c. g., mixed zinc salts of mono-cetyl phosphoric acid and dicetyl phosphoric acid.
The parent esters of the salts of the invention can be prepared by methods :well known in the art. Certain of the parent esters, e. g., monoand dicetyl phosphates and monoand dicholesteryl phosphates are described in the literature. Exemplary methods of preparation are provided by the specific examples below and by Plimmer and Burch, Journal of the Chemical Society, 1929, pages 279-291.
The zinc and cadmium salts can be readily prepared from the parent esters, or from alkali metal salts of the same, by methods well known in the art, as exemplified by the specific examples and by Plimmer and Burch, op. cit.
Examples of salts of the invention are: normal zinc and cadmium mono-amyl phophates, normal zinc ,and cadmium mono-octyl phosphates, normal zinc and cadmium mono-lauryl phosphates, normal zinc and cadmium mono-eicosyl phosphates, normal zinc and cadmium mono-methylcyclohexyl phosphates, normal zinc and cadmium mono-benzyl phosphates and normal zinc and cadmium mono-cetylphenyl phosphates; also, the corresponding normal zinc and cadmium di-amyl, di-octyl, di-lauryl, di-eicosyl, di-methylcyclohexyl, di-benzyl and dicetylphenyl phosphates.
The following specific examples will serve further to illustrate the preparation and properties of the salts of the invention.
EXAMPLE 1 Monoand di-cetyl phosphoric acids and zinc and cadmium salts of the same A mixture of monoand dicetyl phosphoric acids was prepared by reacting 76 parts by weight of cetyl alcohol with a mixture of 17 parts of phosphorus pentoxide and 7 parts of pyrophosphoric acid at 270 F. The phosphorus pentoxide and pyrophosphoric acid were slowly added to the cetyl alcohol. The reaction was complete in two hours.
The two acids were separated by dissolving in hot alcohol (to 20% concentration) and cooling to 40 F., causing precipitation of all the di-ester. The mono-ester was extracted from the alcoholic solution by means of aqueous KOH and the acid was freed by acidification with hydrochloric acid. The dicetyl phosphoric acid was recrystallized twice from ethyl alcohol and once from absolute alcohol. It had a melting point of 63-64.5 C. and analyzed 5.78% phosphorus (theory 5.6%). The monocetyl phosphoric acid analyzed 9.73% phosphorus (theory 9.64%).
Both acids were white crystalline materials, the mono-ester having a flaky appearance and the diester, a granular appearance.
To prepare zinc monocetyl phosphate, the potassium salt was reacted with an equivalent amount of zinc chloride in alcohol solution at 150 F. over a period of 5 hours. The mixture was then cooled to precipitate white zinc monocetyl phosphate, which was washed with hot water to remove potassium chloride and unreacted zinc chloride, as shown by the appearance of only a faint cloud on treating cc. of filtrate with 10 cc. of 0.05 N silver nitrate. The salt was then washed with hot ethyl alcohol and dried in a desiccator at reduced pressure.
To prepare zinc dicetyl phosphate, dicetyl phosphoric acid was reacted with zinc oxide under reflux for 7 hours, in a solvent consisting of two parts by volume of benzene and one of ethyl a1- cohol. The desired salt was obtained as a solid precipitate and was washed with ethyl alcohol and extracted with hot benzene. The benzene was evaporated and the precipitated salt was dried under reduced pressure. Analysis: Found, per cent Zn, 5.9; per cent P, 5.4. Theory, per cent Zn, 5.6; per cent P, 5.4.
Cadmium mono-cetyl phosphate was prepared and purified in the same manner as the corresponding zinc salt, cadmium chloride hydrate eing used in place of zinc chloride. Analysis: Found per cent Cd, 29.1; per cent P, 6.6. Theory, per cent Cd, 25.9; per cent P, 7.2.
Cadmium dicetyl phosphate was prepared by reacting potassium dicetyl phosphate with an equivalent amount of cadmium chloride hydrate in alcohol at 150 F. The solid reaction product was washed with ethyl alcohol, dried, washed with hot benzene, recovered from benzene solution by evaporation of the solvent and dried under reduced pressure.
EXAMPLE 2 Mono-tart. amylphenyl phosphoric acid and zinc and cadmium salts of the same p-Tert. amylphenol was reacted with an equivalent amount of phosphorus pentoxide at 300 F. for 3 hours. The reaction product was purified by recrystallization from petroleum ether to give white, flaky crystals, melting point 210-214 F. The zinc salt was prepared by refluxing one molecular proportion of the acid with 0.68 molecular proportion of zinc oxide in a solvent consisting of two parts by volume of benzene and one of ethyl alcohol for six hours. The solid reaction product was washed with 5% aqueous acetic acid to remove unreacted zinc oxide, then with ethyl alcohol to remove unreacted acid, and dried under reduced pressure.
The cadmium salt was prepared by reacting the potassium salt of mono-p-tert. amylphenyl phosphoric acid with an equivalent amount of cadmium chloride hydrate at F. in ethyl alcohol. The solid reaction product which separated on cooling the mixture to room temperature was washed successively with water and ethyl alcohol to remove potassium chloride, and unreacted cadmium chloride and acid.
Properties of the various salts of the examples are given in Table I below.
These salts were all oil-soluble, the salts of mono-esters being least oil-soluble and the salts of di-esters being most oil-soluble. In general, salts of esters containing a total of at least 20 carbon atoms are freely oil-soluble, those containing less than this being more sparingly oilsoluble.
Interatomic distances of the parent esters, and of the salts of Table I, were determined, establishing the identity of the salts. These interatomic distances, as determined by X-ray diffraction patterns, are as follows:
6 241,648, filed November 31, 1938, since issued on January 14, 1941 as United States Patent No. 2,228,659.
We claim:
1. A zinc salt of an acid ester of ortho phosphoric acid, wherein each esterifying radical is a hydrocarbon group containing not less than 5 carbon atoms.
2. A zinc salt of an acid ester of ortho phosphoric acid, wherein each esterifying radical is a hydrocarbon group containing 5 to 20 carbon atoms, and said salt contains a total of not less than 10 carbon atoms.
3. A zinc salt of an acid ester of ortho phosphoric acid, wherein each esterifying radical is an alkyl hydrocarbon group containing 5 to 20 carbon atoms.
4. A zinc salt of an acid ester of ortho phosphoric acid, wherein each esterifying radical is a cycloaliphatic hydrocarbon group containing 5 to 20 carbon atoms.
5. A zinc salt of an acid ester of ortho phosphoric acid, wherein each esterifying radical is an alliaryl hydrocarbon group containing up to 20 carbon atoms.
6. The salts of claim 2, wherein said acid ester is a mono-ester.
TABLE II Interatomic distances Mono-p-tert. Zn Cd Mono-cetyl Dl-cetyl Zn Cd Zn Cd Compound phosphoric phosphoric $333 1??? mono-cetyl mono-cetyl dicetyl dicet gg fi gg gfigfggggg acid acid acid phosphate phosphate phosphate phosphate phosphate phosphate Distance in Angstrom units (I) and relative line intensities (II) per 0.
Further examples of methods of preparing salts of the invention are as follows:
EXAMPLE 3 Zinc and cadmium dicyclohexyl phophates The parent acid ester is prepared by heating cyclohexanol with phosphorus pentoxide. The salts are prepared by precipitating them from an aqueous solution of the sodium or potassium salt of the parent acid, by addition of cadmium chloride or zinc acetate.
EXAMPLE 4 Zinc and cadmium naphthenyl phosphates These are prepared by reacting naphthenyl alcohols (from reduction of naphthenic acids) with phosphorus pentoxide and precipitation of the desired salts from an aqueous solution of alkali metal salt of the parent acid ester by addition of cadmium chloride or zinc acetate.
This application is a continuation-in-part of our copending application Serial No. 374,245, filed January 13, 1941 (now abandoned) which in turn is a continuation-in-part of application Serial N o. 75 1917, 3rd
7. The salts of claim 2, wherein said acid ester is a di-ester.
BRUCE B. FARRINGTON. JAMES O. CLAYTON. JOHN T. RUTHERFORD.
REFERENCES CITED The following references are of record in the OTHER REFERENCES Plimmer et a1., Jour. Chemical Soc. (London), pgs. 279-291 (1929).
Smiths, Introduction to Inorganic Chemistry,
Ed., pg. 763.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US679262A US2488662A (en) | 1946-06-25 | 1946-06-25 | Metal organo-phosphates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US679262A US2488662A (en) | 1946-06-25 | 1946-06-25 | Metal organo-phosphates |
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| US2488662A true US2488662A (en) | 1949-11-22 |
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| US679262A Expired - Lifetime US2488662A (en) | 1946-06-25 | 1946-06-25 | Metal organo-phosphates |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2784171A (en) * | 1955-06-17 | 1957-03-05 | Monsanto Chemicals | Cadmium alkyl vinyl phosphonate stabilized halogen-containing resin compositions |
| US3157685A (en) * | 1962-03-06 | 1964-11-17 | Stauffer Chemical Co | Partial esters of phosphoric acid and a method of preparing them |
| US3426054A (en) * | 1964-07-16 | 1969-02-04 | Exxon Research Engineering Co | Preparation of metal dialkyl dithiophosphates |
| US3470222A (en) * | 1965-10-05 | 1969-09-30 | Lubrizol Corp | Phosphorus- and metal-containing composition and preparations thereof |
| US3491133A (en) * | 1964-03-06 | 1970-01-20 | Cities Service Res & Dev Co | Metal organo phosphates and amine salts thereof |
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| US1537572A (en) * | 1922-01-21 | 1925-05-12 | Zernik Franz | Base for artificial resins, waxlike substances, and lacquers |
| US2236296A (en) * | 1941-03-25 | Westing and dispersing agent | ||
| US2251798A (en) * | 1937-04-01 | 1941-08-05 | Ig Farbenindustrie Ag | Driers and a process of preparing them |
| US2346155A (en) * | 1942-02-23 | 1944-04-11 | Standard Oil Co | Compounded oil |
| US2360302A (en) * | 1940-08-02 | 1944-10-10 | Standard Oil Co California | Compounded hydrocarbon oil |
| US2409774A (en) * | 1942-10-08 | 1946-10-22 | Advance Solvents & Chemical Co | Drier metal salt and process of making it |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2236296A (en) * | 1941-03-25 | Westing and dispersing agent | ||
| US1537572A (en) * | 1922-01-21 | 1925-05-12 | Zernik Franz | Base for artificial resins, waxlike substances, and lacquers |
| US2251798A (en) * | 1937-04-01 | 1941-08-05 | Ig Farbenindustrie Ag | Driers and a process of preparing them |
| US2360302A (en) * | 1940-08-02 | 1944-10-10 | Standard Oil Co California | Compounded hydrocarbon oil |
| US2346155A (en) * | 1942-02-23 | 1944-04-11 | Standard Oil Co | Compounded oil |
| US2409774A (en) * | 1942-10-08 | 1946-10-22 | Advance Solvents & Chemical Co | Drier metal salt and process of making it |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2784171A (en) * | 1955-06-17 | 1957-03-05 | Monsanto Chemicals | Cadmium alkyl vinyl phosphonate stabilized halogen-containing resin compositions |
| US3157685A (en) * | 1962-03-06 | 1964-11-17 | Stauffer Chemical Co | Partial esters of phosphoric acid and a method of preparing them |
| US3491133A (en) * | 1964-03-06 | 1970-01-20 | Cities Service Res & Dev Co | Metal organo phosphates and amine salts thereof |
| US3426054A (en) * | 1964-07-16 | 1969-02-04 | Exxon Research Engineering Co | Preparation of metal dialkyl dithiophosphates |
| US3470222A (en) * | 1965-10-05 | 1969-09-30 | Lubrizol Corp | Phosphorus- and metal-containing composition and preparations thereof |
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