US2830069A - Process of preparing phosphoric acid esters - Google Patents
Process of preparing phosphoric acid esters Download PDFInfo
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- US2830069A US2830069A US352991A US35299153A US2830069A US 2830069 A US2830069 A US 2830069A US 352991 A US352991 A US 352991A US 35299153 A US35299153 A US 35299153A US 2830069 A US2830069 A US 2830069A
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- United States
- Prior art keywords
- acid
- phosphoric acid
- acid esters
- esters
- preparing phosphoric
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- 238000000034 method Methods 0.000 title description 8
- 150000003014 phosphoric acid esters Chemical class 0.000 title 1
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 description 22
- 150000002148 esters Chemical class 0.000 description 12
- 239000000314 lubricant Substances 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 125000002947 alkylene group Chemical group 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 230000001050 lubricating effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000344 soap Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000004715 keto acids Chemical class 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- -1 hydroxy phos phate Chemical compound 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000907788 Cordia gerascanthus Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- SHBUUTHKGIVMJT-UHFFFAOYSA-N Hydroxystearate Chemical class CCCCCCCCCCCCCCCCCC(=O)OO SHBUUTHKGIVMJT-UHFFFAOYSA-N 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000013531 gin Nutrition 0.000 description 1
- 239000011551 heat transfer agent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 239000010688 mineral lubricating oil Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical class OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 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
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
Definitions
- tion water trap and condenser were placed 100 g. (0.63 m.) C Oxo acid, 98 g. (0.6 equiv.) of the hydroxy phos phate, 100 ml. toluene, and 0.5 g. of p-toluene sulfonic lubricants having outstanding properties of viscosity at iggli g? g i i i ggg low and high temperatures.
- invensolutibnz um neutral a dr'ying it Strippea to tion relates to new and --improved synthetic lubricants 202a/2Vmm which are formed by esterifying the reaction product of an alkylene oxide and phosphoric acid with a long chain aliphatic carboxylic acid.
- This invention relates to synthetic lubricating composi- 15 tions and particularly to new' and irnproved synthetic Example '3.
- a 1' liter fiaskfilled with a reflux condenser connected to a drying tube were-pla'ced' 143 g. (0.64 m.) of a C Oxo acid chlorideiand 98 g? (0.6 equiv.) of hydroxy-phosphate.
- the mixture was refluxed there have been developed entirely new synthetic ma- 3:2 g i gggi fifl g 1233 2 :5222 ggfggifgfi f terials with lubricating properties.
- phosphoric 'acid be Teac-tedflwith, a number of alkylene oxides, The number. of units reacted .withone molecule of' the" acidmayb'e varied within wide ranges. s ""Foi” instance; insteadof"thefethylene'oxideiunitsfutilized h schenent.
- m m Relates a new.type of above;one"may"use'pronylene, butylene o xides, or mixthetlc lubricating composition-which comprises the esters mres Ofe-pdXides; Theln'umberof ufiitsrdaefiwm vary fdepeiiding" upon-the desired'i-no'lecular weight the combustion chamber deposit'sfrom aliiengine already conformula: product as well as the acid to be used to form the esters. It is preferred to use either ethylene oxide or propylene a oxide, however, and to add from about 3 to about l'Z units to each molecule of phosphoric acid.
- R is a monovalent hydrocarbon radical
- R is a
- I1 is a Ill-11111361" from sulting from the reaction of alkylene oxide to phosphoric 1 to 10. acid will have the formula:
- esters of this invention are prepared by reacting O a monocarboxylic aliphatic acid having from 6 to 20 11 carbon atoms per molecule with the reaction product of HO (R'O)FP (OR')"OH an alkylene oxide and phosphoric acid. (0R').0H
- x y and 2 may be the Same or different integers @1166 0 the fOlIOWlHg eXamples, Whlch are to be 6011' It may be desirable to react three, two or one moles sidered as being illustrative only, and are not restrictive of acid with this hydroxy-phosphoric acid, and any numin scope. her up to and including three moles of acid may be used,
- the acid used will ordinarily be a monocarboxylic acid having from about 6 to 20 carbonatoms per molecule and may be of either branched or straight chain configuration.
- Especially preferred, and contemplated in the preferred embodiment of this invention are the highly branched chain acids that are derived from aldehydes or alcohols obtained by subjecting an olefin to the action of carbon monoxide and hydrogen in the Oxo process.
- This process described in detail in U. S. Patent No. 2,367,066, issued to Roelen in 1943, involves the use of temperatures in the order of 150 C. to 350 C. and pressures of about 3000 pounds persquare inch, or higher.
- a cobalt catalyst is used.
- hydrogen is used in conjunction with the carbon monoxide an aldehyde results which may be converted to the acid by oxidation.
- olefins are the polymers or copolymers .of C, and/or C olefins, the resulting polymer and copolymers with other polymerizable materials, such as copolymers of fumarate or maleate esters with vinyl or copolymer having from about 7 to about 16 carbon I atoms.
- Aleohol-dibasic acid hydroxy-phosphate-dtbasle acid-alcohol ibasic acid aleohol may be thickened to grease compositions by using any of the com-,
- the alkali or'alkaline earth metal soaps of high molecular weight substantially saturated fatty acids may be used and the grease compositions prepared by any of the methods withwhich the art is familiar.
- soaps as the oleates, stearates, hydroxy stearates, or ricinoleates of sodium, potassium, lithium, calcium, barium, strontium, aluminum, and the like may be used, as well as the soaps formed by heating animal, fish, or vegetable oils, with soda, lime, baria hydrate or lithia hydrate.
- the synthetic lubricants of invention may be blended with additive agents, such as viscosity index improvers, pour point depressants, detergent inhibitors, oxidation inhibitors, and the like.
- additive agents such as viscosity index improvers, pour point depressants, detergent inhibitors, oxidation inhibitors, and the like.
- Such materials as ester polymers acetate, acrylate or methacrylate polymers or copolymers, phenyl alpha naphthylamine, phenothiazine, 2,6-di-tert.- butyl-para-cresol and many other additive materials may be blended with the synthetic lubricants of this invention.
- esters of invention may also find wide application in a great variety of industrial uses outside the lubricant field.
- these new esters may have utility as plasticizers, solubilizers, heat transfer agents, insecticides, weed killers, r-ust'preventatives,.solvents, dewaxing aids, detergents, oiliness agents as in penetrating oils, and as raw materials for many other industrial applications.
- They may be blended with mineral oils, with other synthetic lubricants such as formals, dibasic acid esters, complex esters, polymerized hydrocarbons, and the like.
- the instant invention relates to new and improved synthetic lubricants which comprise a material of the formula wherein R is an alkyl group containing from 5 to 19 carbon atoms, wherein R represents a divalent hydrocarbon radical containing from 2 to 4 carbon atoms, and
- R may One complex ester so i be alike or ditferent and is preferably branched chain in configuration.
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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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
r 7 2,830,069 7 I; Patented Apr- 1958 PREPARATION OF THEHYDROXY-PHOSPHATE 433mg Example 1.-In a 2 liter 4 necked flask fitted with a thermometer, stirrer, gas inlet bubbler, and condenser, PROCESS F PREPARING PHOSPHORIC were placed 200 g. 1.73 m.) of 85%. H PO and 65 g. ACID ESTERS 5 (0.46 m. of P 0 Ethylene oxidewas bubbled intothe Paul V. Smith, In, Westfield, N. J.', assignor to'E brk mixture with stirring, at such a rate that'the temperature search and Engineering Company, a corporation of s was maintained at 50-60 C., until'a gain in Weight of Delaware 1100 g. was observed. A diluent, such as dioxaneymay beadded if desired. After stripping to constant weight No i fi g g gggi 1953 on-a steam bath, 1315 g. of product was obtainedu Acid, en 0.000 centiequivalent/g., alcohol, 0.608centiequivalent/g. 3 Claims; '(Cl. 260-461) 1 Example 2.In a 1 liter flask fitted with an esterificapositions which have unusual andspecific properties,
tion water trap and condenser were placed 100 g. (0.63 m.) C Oxo acid, 98 g. (0.6 equiv.) of the hydroxy phos phate, 100 ml. toluene, and 0.5 g. of p-toluene sulfonic lubricants having outstanding properties of viscosity at iggli g? g i i i ggg low and high temperatures. More particularly the invensolutibnz um neutral a dr'ying it ,Strippea to tion relates to new and --improved synthetic lubricants 202a/2Vmm which are formed by esterifying the reaction product of an alkylene oxide and phosphoric acid with a long chain aliphatic carboxylic acid.
In recent eflorts to obtain superior lubricating com- This invention relates to synthetic lubricating composi- 15 tions and particularly to new' and irnproved synthetic Example '3.--In a 1' liter fiaskfilled with a reflux condenser connected to a drying tubewere-pla'ced' 143 g. (0.64 m.) of a C Oxo acid chlorideiand 98 g? (0.6 equiv.) of hydroxy-phosphate. The mixture was refluxed there have been developed entirely new synthetic ma- 3:2 g i gggi fifl g 1233 2 :5222 ggfggifgfi f terials with lubricating properties. In general these new L 1 -The-materials prepared according to the inventive-consynthetic lubricants are characterized by vlscoslty properceptlwere submitted to the Standard ASTMYdeterminaties that are outstanding at both low and .high "temperations for flash point, pour point, and 'viscosity. at both tures, especially when compared to mineral-o ls. These 0 R and F Their ASTM slopes Vera-calculated outstandmg low and hlgh temperature Propel-hes tare as were. their viscosity indices: Data are presented in 'pecially desirable for use in equipment designed to opera Table I below ate over a great temperature differential, such as jet e'n gines or turbines'for aircraft use, internal combustion re- Table I ciprocating engine'sfor aircraft and the like. It has been w I foundthat mineral lubricating oils have generallyiundemEste-r v 53g; rslop V I sirable limitations forthelubricationof these:engines 1 -Acid" Value I W. *F. As'rly'r particularly in respect to their :high and low temperature I viscosity characteristics. It has also been found that'synthetic lubricants-may g :32 138 21%}; 8: be desirable for'the lubrication of'stan'dard automotive engines.- In addition to 'the'versatility'of'their' visco'sitybustion chamber deposit formation, particularly when 45. they are used for long periods of times Low rates of I These lubricants may also serve to-reduce or---remoye taining' such'deposits.
- of 'hydroxyphosphoric acid having the foll owing geneljal, I."
The above 'va'lu'es indicate that-the new synthetic lubritempeliature.relanonshlps some types .of'syrithetlczlubri' cents of "invention have outstanding properties oflow cants mvestlgated have another advantage in that-their ,poufpdinfafidrhighfias-h point; Their ASTM slopes and use has been found to result in very low'rates of comviscosity indie-2'5 Show that thes; have eiceuehtvisqsity temperature properties and therefore have outstanding "utili as 'lubricantsfor both low'and hi rtemoerature formation of combustion chamber deposits result in a V more eflicient utilization of fuel, less increase in the Tt'yform..th.hydmxy.compounds used as asmrfin, Octane re'qmremen-t f: an p leis'QPreilgmmn i material-'for'th'e prep'aration of the estersof this inven ency, and an'overall: mprovement in engine operation. tion. phosphoric 'acid be Teac-tedflwith, a number of alkylene oxides, The number. of units reacted .withone molecule of' the" acidmayb'e varied within wide ranges. s ""Foi" instance; insteadof"thefethylene'oxideiunitsfutilized h preisent. m m Relates a new.type of above;one"may"use'pronylene, butylene o xides, or mixthetlc lubricating composition-which comprises the esters mres Ofe-pdXides; Theln'umberof ufiitsrdaefiwm vary fdepeiiding" upon-the desired'i-no'lecular weight the combustion chamber deposit'sfrom aliiengine already conformula: product as well as the acid to be used to form the esters. It is preferred to use either ethylene oxide or propylene a oxide, however, and to add from about 3 to about l'Z units to each molecule of phosphoric acid. wherein R is a monovalent hydrocarbon radical, R is a As was pointed out above, the hydroxy-phesphate re divalent hydrocarbon radical, and I1 is a Ill-11111361" from sulting from the reaction of alkylene oxide to phosphoric 1 to 10. acid will have the formula:
The esters of this invention are prepared by reacting O a monocarboxylic aliphatic acid having from 6 to 20 11 carbon atoms per molecule with the reaction product of HO (R'O)FP (OR')"OH an alkylene oxide and phosphoric acid. (0R').0H
The invention will be more clearlyexplained by referwhere x y and 2 may be the Same or different integers @1166 0 the fOlIOWlHg eXamples, Whlch are to be 6011' It may be desirable to react three, two or one moles sidered as being illustrative only, and are not restrictive of acid with this hydroxy-phosphoric acid, and any numin scope. her up to and including three moles of acid may be used,
- 3 1 depending again upon the properties desired in the finished ester. It may also be desired to add different acids, or use a mixture of acids which may also be done. The acid used will ordinarily be a monocarboxylic acid having from about 6 to 20 carbonatoms per molecule and may be of either branched or straight chain configuration.
Especially preferred, and contemplated in the preferred embodiment of this invention are the highly branched chain acids that are derived from aldehydes or alcohols obtained by subjecting an olefin to the action of carbon monoxide and hydrogen in the Oxo process. This process, described in detail in U. S. Patent No. 2,367,066, issued to Roelen in 1943, involves the use of temperatures in the order of 150 C. to 350 C. and pressures of about 3000 pounds persquare inch, or higher.- A cobalt catalyst is used. When hydrogen is used in conjunction with the carbon monoxide an aldehyde results which may be converted to the acid by oxidation. Further hydrogenation of the aldehyde results in the alcohol which may be converted to the acid by caustic fusion, or other of the well known processes. If water is used instead of hydrogen, the acid results directly from the Oxo process. Preferred olefins are the polymers or copolymers .of C, and/or C olefins, the resulting polymer and copolymers with other polymerizable materials, such as copolymers of fumarate or maleate esters with vinyl or copolymer having from about 7 to about 16 carbon I atoms.
By using as a starting material the reaction product of the alkylene oxide and the phosphoric acid, that is, the hydroxyphosphates and other materials suchas dibasic acids and alcohols, one may build complex molecules which have varying properties. prepared has the following schematic formula:
Aleohol-dibasic acid hydroxy-phosphate-dtbasle acid-alcohol ibasic acid aleohol The, new synthetic lubricants of invention may be thickened to grease compositions by using any of the com-,
mon grease forming soaps. The alkali or'alkaline earth metal soaps of high molecular weight substantially saturated fatty acids may be used and the grease compositions prepared by any of the methods withwhich the art is familiar. ,For instance, such soaps as the oleates, stearates, hydroxy stearates, or ricinoleates of sodium, potassium, lithium, calcium, barium, strontium, aluminum, and the like may be used, as well as the soaps formed by heating animal, fish, or vegetable oils, with soda, lime, baria hydrate or lithia hydrate.
If it is desired to enhance particular properties of the synthetic lubricants of invention, they may be blended with additive agents, such as viscosity index improvers, pour point depressants, detergent inhibitors, oxidation inhibitors, and the like. Such materials as ester polymers acetate, acrylate or methacrylate polymers or copolymers, phenyl alpha naphthylamine, phenothiazine, 2,6-di-tert.- butyl-para-cresol and many other additive materials may be blended with the synthetic lubricants of this invention.
The esters of invention may also find wide application in a great variety of industrial uses outside the lubricant field. For instance, these new esters may have utility as plasticizers, solubilizers, heat transfer agents, insecticides, weed killers, r-ust'preventatives,.solvents, dewaxing aids, detergents, oiliness agents as in penetrating oils, and as raw materials for many other industrial applications. They may be blended with mineral oils, with other synthetic lubricants such as formals, dibasic acid esters, complex esters, polymerized hydrocarbons, and the like.
To reiterate briefly, the instant invention relates to new and improved synthetic lubricants which comprise a material of the formula wherein R is an alkyl group containing from 5 to 19 carbon atoms, wherein R represents a divalent hydrocarbon radical containing from 2 to 4 carbon atoms, and
' wherein x, y, and z are integers of from 1 to 10. R may One complex ester so i be alike or ditferent and is preferably branched chain in configuration.
What is claimed is:
l. A process for preparing an ester of the formula wherein R is a monovalent hydrocarbon radical, R is a divalent hydrocarbon radical of fromZ to 4 carbon atoms and his an integer of from 1 to 10, which com- 3. A process according to claim 1 wherein said alkylene oxide is ethylene oxide and said acid is a C Oxo acid.
References Cited in the file of this patent UNITED STATES PATENTS 2,224,360 Rozenbrocket al. Dec. 3, 1 940 2,365,291 Prutton et a1. Dec. 14, 1944 2,643,261 Matuszak June 23, 1953 FOREIGN PATENTS 452,508 Great Britain Aug. 24, 1936
Claims (1)
1. A PROCESS FOR PREPARING AN ESTER OF THE FORMULA
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US352991A US2830069A (en) | 1953-05-04 | 1953-05-04 | Process of preparing phosphoric acid esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US352991A US2830069A (en) | 1953-05-04 | 1953-05-04 | Process of preparing phosphoric acid esters |
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| Publication Number | Publication Date |
|---|---|
| US2830069A true US2830069A (en) | 1958-04-08 |
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|---|---|---|---|
| US352991A Expired - Lifetime US2830069A (en) | 1953-05-04 | 1953-05-04 | Process of preparing phosphoric acid esters |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2979523A (en) * | 1956-03-06 | 1961-04-11 | Gulf Oil Corp | Addition products of dialkyl acid orthophosphate and olefin oxides |
| US2979478A (en) * | 1958-04-01 | 1961-04-11 | Virginia Carolina Chem Corp | Composition containing polyvinyl alcohol and a neutral ester of phosphoric acid |
| US2982685A (en) * | 1957-12-23 | 1961-05-02 | Shell Oil Co | Arylphosphate compounds |
| US2982686A (en) * | 1957-12-23 | 1961-05-02 | Shell Oil Co | Arylphosphate compounds |
| US2990421A (en) * | 1958-04-01 | 1961-06-27 | Virginia Carolina Chem Corp | Neutral esters of phosphoric acid |
| US3061625A (en) * | 1961-06-15 | 1962-10-30 | Weston Chemical Corp | Phosphates and thiophosphates |
| US3094549A (en) * | 1961-07-27 | 1963-06-18 | Dow Chemical Co | Process for preparing hydroxyalkyl phosphates |
| US3121106A (en) * | 1960-03-30 | 1964-02-11 | Manufactures De Prod Chim De N | Preparation of halogen substituted phosphoric acid esters |
| US3153080A (en) * | 1961-01-31 | 1964-10-13 | Eastman Kodak Co | Acyloxyneopentyl and acyloxycyclobutane phosphate partial esters |
| US3184497A (en) * | 1963-03-25 | 1965-05-18 | Hercules Powder Co Ltd | Tris(dihydroxyalkyl) phosphates |
| US3202693A (en) * | 1962-10-11 | 1965-08-24 | Monsanto Co | Succinate half-esters of alkylene glycol phosphate |
| US3256240A (en) * | 1960-11-10 | 1966-06-14 | Union Carbide Corp | Compositions comprising a polyepoxide, a chloro-hydroxy hydrocarbon phosphate and anepoxy resin curing agent |
| US3267049A (en) * | 1960-08-26 | 1966-08-16 | Bayer Ag | Phosphorus polyurethane plastic prepared from a hydroxyl phosphorus compound |
| US3309427A (en) * | 1963-01-15 | 1967-03-14 | Atlas Chemicals Ind Inc | Polyhydroxy phosphate esters |
| US3441544A (en) * | 1962-07-10 | 1969-04-29 | Richardson Co | Phosphoric acid esters and polymers thereof |
| US3470222A (en) * | 1965-10-05 | 1969-09-30 | Lubrizol Corp | Phosphorus- and metal-containing composition and preparations thereof |
| US3976494A (en) * | 1973-12-27 | 1976-08-24 | Onoda Cement Company, Ltd. | Process for inhibiting corrosion of iron or steel placed in cement products |
| US20050272912A1 (en) * | 2004-06-03 | 2005-12-08 | Eleveld Michiel B | Process for the preparation of polyether polyols |
| WO2018046586A1 (en) | 2016-09-09 | 2018-03-15 | Covestro Deutschland Ag | Porous materials based on polyurethane/polyisocyanurate and production and use thereof |
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| GB452508A (en) * | 1934-01-24 | 1936-08-24 | Chemische Fabriek Servo Nv | A process of manufacturing washing, cleansing, wetting and emulsifying agents and treatment baths containing the same |
| US2224360A (en) * | 1936-08-26 | 1940-12-10 | Naamlooze Vennootschap Chemisc | Process of manufacturing washing, cleansing, wetting, and emulsifying agents |
| US2365291A (en) * | 1941-05-26 | 1944-12-19 | Lubri Zol Corp | Stabilizing agents for hydrocarbon compositions and the like |
| US2643261A (en) * | 1948-10-01 | 1953-06-23 | Standard Oil Dev Co | Phosphorus-containing lubricating oil additives |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB452508A (en) * | 1934-01-24 | 1936-08-24 | Chemische Fabriek Servo Nv | A process of manufacturing washing, cleansing, wetting and emulsifying agents and treatment baths containing the same |
| US2224360A (en) * | 1936-08-26 | 1940-12-10 | Naamlooze Vennootschap Chemisc | Process of manufacturing washing, cleansing, wetting, and emulsifying agents |
| US2365291A (en) * | 1941-05-26 | 1944-12-19 | Lubri Zol Corp | Stabilizing agents for hydrocarbon compositions and the like |
| US2643261A (en) * | 1948-10-01 | 1953-06-23 | Standard Oil Dev Co | Phosphorus-containing lubricating oil additives |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2979523A (en) * | 1956-03-06 | 1961-04-11 | Gulf Oil Corp | Addition products of dialkyl acid orthophosphate and olefin oxides |
| US2982685A (en) * | 1957-12-23 | 1961-05-02 | Shell Oil Co | Arylphosphate compounds |
| US2982686A (en) * | 1957-12-23 | 1961-05-02 | Shell Oil Co | Arylphosphate compounds |
| US2979478A (en) * | 1958-04-01 | 1961-04-11 | Virginia Carolina Chem Corp | Composition containing polyvinyl alcohol and a neutral ester of phosphoric acid |
| US2990421A (en) * | 1958-04-01 | 1961-06-27 | Virginia Carolina Chem Corp | Neutral esters of phosphoric acid |
| US3121106A (en) * | 1960-03-30 | 1964-02-11 | Manufactures De Prod Chim De N | Preparation of halogen substituted phosphoric acid esters |
| US3267049A (en) * | 1960-08-26 | 1966-08-16 | Bayer Ag | Phosphorus polyurethane plastic prepared from a hydroxyl phosphorus compound |
| US3256240A (en) * | 1960-11-10 | 1966-06-14 | Union Carbide Corp | Compositions comprising a polyepoxide, a chloro-hydroxy hydrocarbon phosphate and anepoxy resin curing agent |
| US3153080A (en) * | 1961-01-31 | 1964-10-13 | Eastman Kodak Co | Acyloxyneopentyl and acyloxycyclobutane phosphate partial esters |
| US3061625A (en) * | 1961-06-15 | 1962-10-30 | Weston Chemical Corp | Phosphates and thiophosphates |
| US3094549A (en) * | 1961-07-27 | 1963-06-18 | Dow Chemical Co | Process for preparing hydroxyalkyl phosphates |
| US3441544A (en) * | 1962-07-10 | 1969-04-29 | Richardson Co | Phosphoric acid esters and polymers thereof |
| US3202693A (en) * | 1962-10-11 | 1965-08-24 | Monsanto Co | Succinate half-esters of alkylene glycol phosphate |
| US3309427A (en) * | 1963-01-15 | 1967-03-14 | Atlas Chemicals Ind Inc | Polyhydroxy phosphate esters |
| US3184497A (en) * | 1963-03-25 | 1965-05-18 | Hercules Powder Co Ltd | Tris(dihydroxyalkyl) phosphates |
| US3470222A (en) * | 1965-10-05 | 1969-09-30 | Lubrizol Corp | Phosphorus- and metal-containing composition and preparations thereof |
| US3976494A (en) * | 1973-12-27 | 1976-08-24 | Onoda Cement Company, Ltd. | Process for inhibiting corrosion of iron or steel placed in cement products |
| US20050272912A1 (en) * | 2004-06-03 | 2005-12-08 | Eleveld Michiel B | Process for the preparation of polyether polyols |
| US7300993B2 (en) | 2004-06-03 | 2007-11-27 | Shell Oil Company | Process for the preparation of polyether polyols |
| WO2018046586A1 (en) | 2016-09-09 | 2018-03-15 | Covestro Deutschland Ag | Porous materials based on polyurethane/polyisocyanurate and production and use thereof |
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