US2656375A - Amino bicyclohexyl-alkyl acid phosphate reaction product - Google Patents
Amino bicyclohexyl-alkyl acid phosphate reaction product Download PDFInfo
- Publication number
- US2656375A US2656375A US245429A US24542951A US2656375A US 2656375 A US2656375 A US 2656375A US 245429 A US245429 A US 245429A US 24542951 A US24542951 A US 24542951A US 2656375 A US2656375 A US 2656375A
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- US
- United States
- Prior art keywords
- oil
- amino
- bicyclohexyl
- reaction product
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910019142 PO4 Inorganic materials 0.000 title claims description 37
- 239000002253 acid Substances 0.000 title claims description 28
- 239000010452 phosphate Substances 0.000 title claims description 25
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims description 21
- 239000007795 chemical reaction product Substances 0.000 title description 22
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title description 2
- SHCFCJUJGBRSPO-UHFFFAOYSA-N 1-cyclohexylcyclohexan-1-amine Chemical compound C1CCCCC1C1(N)CCCCC1 SHCFCJUJGBRSPO-UHFFFAOYSA-N 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000002480 mineral oil Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000002401 inhibitory effect Effects 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000003921 oil Substances 0.000 description 38
- 235000019198 oils Nutrition 0.000 description 37
- 235000021317 phosphate Nutrition 0.000 description 35
- 239000003112 inhibitor Substances 0.000 description 21
- 125000000217 alkyl group Chemical group 0.000 description 20
- -1 AMINO Chemical class 0.000 description 19
- 230000003647 oxidation Effects 0.000 description 17
- 238000007254 oxidation reaction Methods 0.000 description 17
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 12
- 150000001412 amines Chemical class 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 239000000839 emulsion Substances 0.000 description 9
- 239000000314 lubricant Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000002199 base oil Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical group CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000010723 turbine oil Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- JTXUVYOABGUBMX-UHFFFAOYSA-N didodecyl hydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCC JTXUVYOABGUBMX-UHFFFAOYSA-N 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- HNOYVXSMDIKYFF-UHFFFAOYSA-N butan-1-amine dodecan-1-amine Chemical compound C(CCCCCCCCCCC)N.C(CCC)N HNOYVXSMDIKYFF-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000011005 laboratory method Methods 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- XHRCFGDFESIFRG-UHFFFAOYSA-N 2-chloro-n-ethyl-n-[(2-methylphenyl)methyl]ethanamine Chemical compound ClCCN(CC)CC1=CC=CC=C1C XHRCFGDFESIFRG-UHFFFAOYSA-N 0.000 description 1
- KEHCTKVZDAEDPP-UHFFFAOYSA-N 2-cyclohexylcyclohexan-1-amine Chemical compound NC1CCCCC1C1CCCCC1 KEHCTKVZDAEDPP-UHFFFAOYSA-N 0.000 description 1
- TYLZNTKFVQUEQJ-UHFFFAOYSA-N 3-benzhydrylbenzene-1,2-diamine Chemical compound NC=1C(=C(C=CC1)C(C1=CC=CC=C1)C1=CC=CC=C1)N TYLZNTKFVQUEQJ-UHFFFAOYSA-N 0.000 description 1
- IMPPGHMHELILKG-UHFFFAOYSA-N 4-ethoxyaniline Chemical compound CCOC1=CC=C(N)C=C1 IMPPGHMHELILKG-UHFFFAOYSA-N 0.000 description 1
- 241000331231 Amorphocerini gen. n. 1 DAD-2008 Species 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- JJCFRYNCJDLXIK-UHFFFAOYSA-N cyproheptadine Chemical compound C1CN(C)CCC1=C1C2=CC=CC=C2C=CC2=CC=CC=C21 JJCFRYNCJDLXIK-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 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
- 239000003346 palm kernel oil Substances 0.000 description 1
- 235000019865 palm kernel oil Nutrition 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000004448 titration Methods 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
-
- 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
- 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
- C10M2223/043—Ammonium or amine 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/135—Steam engines or turbines
-
- 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
- C10N2070/00—Specific manufacturing methods for lubricant compositions
- C10N2070/02—Concentrating of additives
Definitions
- This invention relates to an amino bicyclohexyl reaction product and. the means for manufacturing the same. More particularly it relates to the product formed by the reaction between an alkyl acid phosphate and amino bicyclohexyl, and to processes for its manufacture.
- the reaction product described herein is useful as a surface active agent, an oiliness agent, a mild extreme pressure agent, a rust and corrosion inhibitor, and the like. It is especially valuable as a corrosion inhibitor for lubricating oils, particularly for use in connection with the lubrication of steam turbines and other marine gear where severe conditions conducive to rusting are normally encountered. It is also useful in various other lubricants, especially where rusting conditions are encountered such as, for example, in internal combustion engines, air compressors, and so forth.
- the product has various advantages over the reaction products of other amines and alkyl phosphates.
- the present invention provides an inhibitor for hydrocarbon oil having enhanced rust-inhibiting properties with freedom from substantial emulsion-forming tendency and of complete compatibility with the oil and with conventional oxidation inhibitors.
- the inhibitor When blended in proper proportions with an otherwise suitable base oil, the inhibitor provides a turbine oil meeting the severerequirements of the U. 8. Navy specifications.
- the product of the presentinvention is the re action product of an amino bicyclohexyl with an alkyl acid phosphate having from 8 to 16 carbon atoms per alkyl group.
- amino bicyclo hexyls the ortho and meta amino bicycloh-exyls are preferred.
- This primary amine is sometimes called cyclohexyl-cyclohexylamine, the ortho isomer being 'sdesignat'ed as 2-cyclohexylcyclo hexylamine and the meta isomer as 3-cyclohexylcyclohe'xylamine.
- the preferred alkyl phosphate is Lorol" acid phosphate, WhiOhiS a mixture of phosphoric esters of Lorol alcohol.
- Lorol alcohol is used in the trade to denote a mixture of primary normal aliphatic alcohols of 8 to .12 carbon atoms which are obtained by fractionation of'the alcohols resulting from the reduction of cocoanut and/or palm kernel oils. Loro1" acid phosphate-mixtures are readily. obtainable on the market and for this reason are preferred to the more purified esters of greater scarcity and higher price.
- Lorol acid phosphate type is .soldnnder thetrade name Ortholeum 162 and isunderstoodto be mainly a mixture ofthe mono and di acid phosphates of Lorol alcohol? Although for the'reasons stated 'above"Lorol acid phosphates are preferred, other alkyl acid phosphates containing from 8 to 16 carbon atoms per alkyl group are satisfactory.
- the di-alkyl phosphates are preferred, although the commercial grade containing significant amounts of mono-alkyl phosphates are entirely suitable.
- organic amines tend to form with mono-alkyl phosphatessmall amounts of reaction products of unknown composition which are oil-insoluble and thus produce undesirable precipitates when used in mineral oils. However, with the amino bicyclohexyl of the present invention this tendency is not exhibited, thereby permitting the use of commercial grades of dialkyl phosphates without the formation of objectionable precipitate or doc.
- the reaction product of amino bicyclohexyl may be manufactured either as an'oil-free product, as an oil concentrate, or in situ with a base oil. It may be considered as an addition salt resulting from the neutralization of the acidity of the alkyl acid phosphate by the basicity of the amine. Since the alkyl acid phosphate comprises mono and di alkyl acid phosphates and'the alkyl groups vary from C8 to C12 in chain length, the reaction product cannot be represented by any one clear-cut structural formula. However it is a well defined clear reddish yellow viscous oil which shows no indication of crystallizing on standing and readily forms oil concentrates such as 5% and 50% solutions. I
- Substantially pure amino bicyclohexyl such as is available commercially, may be used to form the reaction product.
- This material isadvantageously'preheated above. 212 F., preferably in the range of 250 F. to 270 F., prior to contactme with the alkyl acid phosphate in order to prevent the formation of a 11% which might otherwise occur.
- a general process for manufacturing the reaction product comprises contacting predetermined quantities of amino bicyclohexyl with alkyl acid phosphate at a temperature within the-range of to 200 F. with vigorous agitation for a period of several hours. The reaction normally proceeds rapidly with'the evolution ofheat, and a clear reddish yellow product results.
- the proper proportions of amino bicyclohexyl to alkyl acid phosphate may readily vbe determined by an electrometric titration of. a sample of the acid alkyl phosphate with, aqueous KOH solution to a pH of about 9. From the amount of KOH used theamount of the amino bicyclohexyl required to neutralize theacid radicals of. the phosphate may be readily calculated, It is desirable to have a slight excess of amine present; however, good results have been obtained with from 25% deficiency up to 50% excess of amine.
- reaction product of the invention may be prepared by mixing the alkyl acid phosphate selected with amino bicyclohexyl in stoichiometric proportions and the resulting product added to the base oil, it is convenient to add the ingredients to at least a portion of the base oil and permit the reaction to occur in the oil. A certain amount of heat, say up to about 175 F., will assist in the ready formation of the reaction product, taking care not to heat the uncombined alkyl phosphate to a temperature where decomposition of the same is initiated.
- Example I About 250 grams of a mixture of the mono and 'di alkyl acid phosphates comprising an approxiand heated to 130 F. While stirring vigorously,
- the reaction product of the invention appears to be soluble in mineral oil in practically all proportions, and it is within the broad scope of the invention to prepare the reaction product, or a concentrate thereof, in mineral oil for subsequent use as a compounding agent for any desired oil.
- the reaction product is compatible with oxidation inhibitors, even with aromatic primary amine oxidation inhibitors which frequently cause floc formation in oils containing amine salts of alkyl phosphate esters. It is also compatible with pour depressants, viscosity index improvers and anti-foam agents. Accordingly, it is also within the scope of the invention,-
- the requirements of the lubricants employed are most exacting since the lubricant comes in contact with condensed steam and, at times, even with sea water due to leaks in the condensing and cooling systems.
- the lubricant must separate successfully from the Water without the formation of troublesome emulsions and must be able substantially to protect the metal surfaces of the turbines from rust even under these severe conditions.
- the rust protection is needed not only by those parts continually wetted by the oil, but also by those parts of the system which are not continually flooded by the oil.
- the lubricant must not foam to any substantial extent. Also. for commercial reasons, the lubricant should be entirely homogeneous and free from suspended matter and compatible with other additives such as oxidation inhibitors.
- Paragraph lit-4 of the above Navy pamphlet re quires that any additive agents used must remain uniformly distributed in the oil, i. e. there shall be no separation of a solid phase from the oil.
- F100 also appears in some otherwise satisfactory oils upon the addition thereto of an oxidation inhibitor, particularly when the oxidation inhibitor is an aromatic primary amine such, as for example, paraphenylene diamine, toluene diamine, diamino triphenyl methane, alkoxy anilines, and the like.
- the oxidation inhibitor is an aromatic primary amine such, as for example, paraphenylene diamine, toluene diamine, diamino triphenyl methane, alkoxy anilines, and the like.
- a turbine oil since it is desirable for a turbine oil to contain an oxidation inhibitor as well as a rust inhibitor, and since these aromatic amines are otherwise excellent oxidation inhibitors, it is highly important to choose a rust inhibitor which not only is free from floc formation when used alone but is also free from floc formation when used in conjunction with oxidation inhibitors, either compounded therewith originally or added later (for example, by the customer or distributor).
- turbine oils may be prepared which overcome the above disadvantages of other additives and satisfactorily meet the Navy specifications.
- the base oil may be any refined mineral oil of otherwise suitable properties.
- the base oil may be a 50 V. I. solvent refined hydrocarbon oil having a Saybolt viscosity at 130 F. of 185-205 seconds and having suitable anti-emulsion characteristics.
- a small but eifective amount of the above described reaction product For some anti-rust uses as little as 0.01% by weight of the reaction product may be used. However, for satisfactorily meeting the Navy specifications for a turbine oil, at least 5 0.02%, and preferably at least 0.03%, by weight should be used. The inhibitor has been found to be satisfactory in amounts up to 0.15% by weight and is believed to be satisfactory in even greater amounts although the additional cost may not be justified by any additional eifectiveness.
- Example III Oil prepared as in Example II was tested and found to pass the Navy corrosion test and emulsion tests. No insoluble precipitate or floc occurred in the oil even after several months storage.
- Example IV Oil prepared as in Example II was heated to 150 F. and 0.25% by weight of an oxidation inhibitor (2,6-ditertiarybutyl-4-methylphenol) was added with stirring. The resulting oil again passed the Navy corrosion test and emulsion tests and showed no precipitate or floc after several months storage. This oil showed excellent oxidation stability when tested by various laboratory methods.
- an oxidation inhibitor (2,6-ditertiarybutyl-4-methylphenol)
- Example-V c011 pheparedasiEExamplejII was heated;- to 15'0?F. and 0.25%..by weight of an; oxidation inhibitor (para. phen'etidi'nei wasaddediwith stirring. Theresulting oil again passed the Navy corrosion test and emulsion tests and showed no precipitate or floc after several months storage. This oilishowed excellent oxidation stability when tested. by various. laboratory methods.
- Di-octadecylami Tri-amylarnine Di 2-Ethyl Hcxyla Cyclohexylainine Di-cyclohexylamine Paraphenetidine Aniline Amino bicyclohexyl Wlgh 0.25% Oxidation Inhib' N-Butylamine Dodecylamine... Hexadecylamine Di-2-Ethyl Hexylamme...
- V mono and di-phosphoric acid esters of the several aliphatic alcohols from octyl to hexadecyl alcohol may be used, mixtures of these are generally more readily available commercially. Such mixtures are intended to be included within the scope of the term alkyl acid phosphate as used in the claims and the word phosphate is intended to include a single phosphate or a plurality of the same unless otherwise specifically indicated.
- alkyl. acid phosphate is a mixture of phosphoric acidesters of fatty alcohols of 8 to 12 carbon atoms derived from cocoanut and palm oils.
- a process for the manufacture of the addition product of amino bicyclohexyl and alkyl acid phosphate which comprises: heating amino bicyclohexyl to a temperature between 212 and 270 F., then cooling and subsequently reactin said amine with alkyl acid phosphate having from 8 to 16 carbon atoms per alkyi group while maintaining the reaction temperature between 100 and 200 F.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Lubricants (AREA)
Description
Patented Oct. 20, 1953 AMINO BICYCLOHEXYL-ALKYL ACID PHOS- PHATE REACTION PRODUCT Samuel Clyde Vaughn, Berkeley, Calif., assignor ,to Tide Water Associated Oil Company, San
Francisco, Calif., a corporation ofDelaware No Drawing; Application September 6, 1951-,
Serial No. 245,429
Claims.. 1
.This invention relates to an amino bicyclohexyl reaction product and. the means for manufacturing the same. More particularly it relates to the product formed by the reaction between an alkyl acid phosphate and amino bicyclohexyl, and to processes for its manufacture.
The reaction product described herein is useful as a surface active agent, an oiliness agent, a mild extreme pressure agent, a rust and corrosion inhibitor, and the like. It is especially valuable as a corrosion inhibitor for lubricating oils, particularly for use in connection with the lubrication of steam turbines and other marine gear where severe conditions conducive to rusting are normally encountered. It is also useful in various other lubricants, especially where rusting conditions are encountered such as, for example, in internal combustion engines, air compressors, and so forth. The product :has various advantages over the reaction products of other amines and alkyl phosphates.
The present inventionprovides an inhibitor for hydrocarbon oil having enhanced rust-inhibiting properties with freedom from substantial emulsion-forming tendency and of complete compatibility with the oil and with conventional oxidation inhibitors. When blended in proper proportions with an otherwise suitable base oil, the inhibitor provides a turbine oil meeting the severerequirements of the U. 8. Navy specifications.
The product of the presentinvention is the re action product of an amino bicyclohexyl with an alkyl acid phosphate having from 8 to 16 carbon atoms per alkyl group. Of the amino bicyclo hexyls the ortho and meta amino bicycloh-exyls are preferred. This primary amine is sometimes called cyclohexyl-cyclohexylamine, the ortho isomer being 'sdesignat'ed as 2-cyclohexylcyclo hexylamine and the meta isomer as 3-cyclohexylcyclohe'xylamine. Mainly for commercial reasons, the preferred alkyl phosphate is Lorol" acid phosphate, WhiOhiS a mixture of phosphoric esters of Lorol alcohol. The term Lorol alcohol is used in the trade to denote a mixture of primary normal aliphatic alcohols of 8 to .12 carbon atoms which are obtained by fractionation of'the alcohols resulting from the reduction of cocoanut and/or palm kernel oils. Loro1" acid phosphate-mixtures are readily. obtainable on the market and for this reason are preferred to the more purified esters of greater scarcity and higher price. One Lorol acid phosphate type is .soldnnder thetrade name Ortholeum 162 and isunderstoodto be mainly a mixture ofthe mono and di acid phosphates of Lorol alcohol? Although for the'reasons stated 'above"Lorol acid phosphates are preferred, other alkyl acid phosphates containing from 8 to 16 carbon atoms per alkyl group are satisfactory. The di-alkyl phosphates are preferred, although the commercial grade containing significant amounts of mono-alkyl phosphates are entirely suitable. Generally organic amines tend to form with mono-alkyl phosphatessmall amounts of reaction products of unknown composition which are oil-insoluble and thus produce undesirable precipitates when used in mineral oils. However, with the amino bicyclohexyl of the present invention this tendency is not exhibited, thereby permitting the use of commercial grades of dialkyl phosphates without the formation of objectionable precipitate or doc.
The reaction product of amino bicyclohexyl may be manufactured either as an'oil-free product, as an oil concentrate, or in situ with a base oil. It may be considered as an addition salt resulting from the neutralization of the acidity of the alkyl acid phosphate by the basicity of the amine. Since the alkyl acid phosphate comprises mono and di alkyl acid phosphates and'the alkyl groups vary from C8 to C12 in chain length, the reaction product cannot be represented by any one clear-cut structural formula. However it is a well defined clear reddish yellow viscous oil which shows no indication of crystallizing on standing and readily forms oil concentrates such as 5% and 50% solutions. I
Substantially pure amino bicyclohexyl, such as is available commercially, may be used to form the reaction product. This material. isadvantageously'preheated above. 212 F., preferably in the range of 250 F. to 270 F., prior to contactme with the alkyl acid phosphate in order to prevent the formation of a 11% which might otherwise occur. A general process for manufacturing the reaction product comprises contacting predetermined quantities of amino bicyclohexyl with alkyl acid phosphate at a temperature within the-range of to 200 F. with vigorous agitation for a period of several hours. The reaction normally proceeds rapidly with'the evolution ofheat, and a clear reddish yellow product results.
The proper proportions of amino bicyclohexyl to alkyl acid phosphate may readily vbe determined by an electrometric titration of. a sample of the acid alkyl phosphate with, aqueous KOH solution to a pH of about 9. From the amount of KOH used theamount of the amino bicyclohexyl required to neutralize theacid radicals of. the phosphate may be readily calculated, It is desirable to have a slight excess of amine present; however, good results have been obtained with from 25% deficiency up to 50% excess of amine.
Although the reaction product of the invention may be prepared by mixing the alkyl acid phosphate selected with amino bicyclohexyl in stoichiometric proportions and the resulting product added to the base oil, it is convenient to add the ingredients to at least a portion of the base oil and permit the reaction to occur in the oil. A certain amount of heat, say up to about 175 F., will assist in the ready formation of the reaction product, taking care not to heat the uncombined alkyl phosphate to a temperature where decomposition of the same is initiated.
Example I About 250 grams of a mixture of the mono and 'di alkyl acid phosphates comprising an approxiand heated to 130 F. While stirring vigorously,
250 grams of ortho amino bicyclohexyl, preheated to 265 F. and cooled to room temperature, was
added and the mixture thoroughly agitated for two hours. During this time the temperature rose to 190 F. A clear reddish yellow viscous oil reaction product resulted therefrom.
The reaction product of the invention appears to be soluble in mineral oil in practically all proportions, and it is within the broad scope of the invention to prepare the reaction product, or a concentrate thereof, in mineral oil for subsequent use as a compounding agent for any desired oil. The reaction product is compatible with oxidation inhibitors, even with aromatic primary amine oxidation inhibitors which frequently cause floc formation in oils containing amine salts of alkyl phosphate esters. It is also compatible with pour depressants, viscosity index improvers and anti-foam agents. Accordingly, it is also within the scope of the invention,-
broadly speaking, to include in the concentrate (or in the finished oil) desired amounts of an oxidation inhibitor.
U. S. Govt Emulsion Test 130 F.
Distilled water (minutes for separation) 1% NaCl (minutes for separation) 10 Carbon residue, percent 0.10 Sulfur, percent 0.31
was heated to 250 F. Into the heated oil was stirred 0.015% by weight of ortho amino bicyclohexyl. The resulting mixture was cooled to 175 F. after which there was added 0.015% by wei ht of Ortholeum 162 (stoichiometric amount) The reaction mixture was then stirred vigorously for 2 hours and allowed to stand for 16 hours, resulting in an oil containing the reaction product Of the invention.
To illustrate the superior utility of the reaction product when used in turbine oils, the following discussion is presented.
In the lubrication of modern steam turbines the requirements of the lubricants employed are most exacting since the lubricant comes in contact with condensed steam and, at times, even with sea water due to leaks in the condensing and cooling systems. The lubricant must separate successfully from the Water without the formation of troublesome emulsions and must be able substantially to protect the metal surfaces of the turbines from rust even under these severe conditions. The rust protection is needed not only by those parts continually wetted by the oil, but also by those parts of the system which are not continually flooded by the oil. The lubricant must not foam to any substantial extent. Also. for commercial reasons, the lubricant should be entirely homogeneous and free from suspended matter and compatible with other additives such as oxidation inhibitors.
In order to insure proper performance from oils supplied for marine steam turbines, the U. S. Navy has adopted rigid specifications set forth in the 'Navy Department specification pamphlet 14-0-15 dated August 15, 1945. Among the important tests of these specifications is the test for Corrosion (in the presence of salt water) described therein in paragraphs E5 and F-3C. In brief, this corrosion test provides that a polished cylindrical steel specimen shall show no corrosion when partially immersed for 48 hours in a bath composed of 300 ml. of oil and ml. of
' synthetic sea water maintained at 140 F. This test is recognized by the Navy as a means of indicating the degree of protection against rust afforded by a lubricant under test.
Another important test provided by the above mentioned Navy specifications is the emulsion test. Briefly, in this test 40 ml. of the oil under test and 40 ml. of distilled water are stirred together at 1500 R. P. M. in a ml. graduate at F. for 5 minutes after which the oil must separate satisfactorily from the water in 30 minutes. The test is repeated using 1% NaCl solution instead of distilled water.
Paragraph lit-4 of the above Navy pamphlet re quires that any additive agents used must remain uniformly distributed in the oil, i. e. there shall be no separation of a solid phase from the oil.
Many rust-inhibiting lubricants have been proposed for use in steam turbines. A large propor tion of these are composed of well refined mineral 3 oil to which has been added small quantities of alkyl phosphate esters. Improved results are claimed by many when acid alkyl phosphates are used and the acid radical is neutralized with a slight excess of an organic amine, for which purpose various amines have been suggested. In general, these lubricants have given more or less satisfactory results in steam turbines. However, most of them fail to meet the rigid Navy specifications for one or more of the following reasons:
(a) When tested by the severe Navy corrosion test, rusting occurs on that portion of the steel specimen not immersed in the oil bath, or at the surface of the oil, indicating that the oil is somewhat deficient in the protection afforded to those parts of the turbine not continually wetted by the oil.
(b) The particular amine used to neutralize the acid alkyl phosphate, or the resulting compound, is conducive to the formation of emulamassesionsw-itl'r either salt'water-of distilled water; and the compounded oil fails to meet the-Navy'-'-emulsion-requirementsasindicated by the emulsion test mentioned above.
ic)-:;A-light fiocculen't. precipitate; or ifflo'cfii appears in thereon-within a fewdayaaiter its preparation. Although this'fioc may'n'ot be of any speciaF disadvantage in the actual oper'ati'on of the-turbinefit greatlyatfects customer acceptance of the-oil and isunacceptable by many; including the-'- Navy. This floc phenomenon occurs -with many of-theamines proposed especially ==when mono-alkylacidphosphates are used =or' with commercial di-alkyl phosphates which invariably contain significant amounts of mono-alkyl phosphates. F100 also appears in some otherwise satisfactory oils upon the addition thereto of an oxidation inhibitor, particularly when the oxidation inhibitor is an aromatic primary amine such, as for example, paraphenylene diamine, toluene diamine, diamino triphenyl methane, alkoxy anilines, and the like. Since it is desirable for a turbine oil to contain an oxidation inhibitor as well as a rust inhibitor, and since these aromatic amines are otherwise excellent oxidation inhibitors, it is highly important to choose a rust inhibitor which not only is free from floc formation when used alone but is also free from floc formation when used in conjunction with oxidation inhibitors, either compounded therewith originally or added later (for example, by the customer or distributor).
By the use of the reaction product of the pres ent invention, turbine oils may be prepared which overcome the above disadvantages of other additives and satisfactorily meet the Navy specifications.
In the preparation of such a turbine oil the base oil may be any refined mineral oil of otherwise suitable properties. For example, the base oil may be a 50 V. I. solvent refined hydrocarbon oil having a Saybolt viscosity at 130 F. of 185-205 seconds and having suitable anti-emulsion characteristics.
Into the base oil is incorporated a small but eifective amount of the above described reaction product. For some anti-rust uses as little as 0.01% by weight of the reaction product may be used. However, for satisfactorily meeting the Navy specifications for a turbine oil, at least 5 0.02%, and preferably at least 0.03%, by weight should be used. The inhibitor has been found to be satisfactory in amounts up to 0.15% by weight and is believed to be satisfactory in even greater amounts although the additional cost may not be justified by any additional eifectiveness.
Example III Oil prepared as in Example II was tested and found to pass the Navy corrosion test and emulsion tests. No insoluble precipitate or floc occurred in the oil even after several months storage.
Example IV Oil prepared as in Example II was heated to 150 F. and 0.25% by weight of an oxidation inhibitor (2,6-ditertiarybutyl-4-methylphenol) was added with stirring. The resulting oil again passed the Navy corrosion test and emulsion tests and showed no precipitate or floc after several months storage. This oil showed excellent oxidation stability when tested by various laboratory methods.
Example-V c011 pheparedasiEExamplejII was heated;- to 15'0?F. and 0.25%..by weight of an; oxidation inhibitor (para. phen'etidi'nei wasaddediwith stirring. Theresulting oil again passed the Navy corrosion test and emulsion tests and showed no precipitate or floc after several months storage. This oilishowed excellent oxidation stability when tested. by various. laboratory methods.
"To :Eurther'illustratelthe superior properties of turbine oilscompoundedwith the rustinhibitor or the presentlinvention, the followingv table is given "showing comparative tests with the same base oil compounded with approximately 0.03% of the reaction products of Ortholeum 162 with various representative amines. The table shows results with and without an oxidation inhibitor (para phenetidine) Navy Sea Navy P Amine Used Water Cor- Emulsion rosion Test Test Formatwn Without Oxidation Inhibitor:
N -Butylamine Dodecylamine.
Di-octadecylami Tri-amylarnine Di 2-Ethyl Hcxyla Cyclohexylainine Di-cyclohexylamine Paraphenetidine Aniline Amino bicyclohexyl Wlgh 0.25% Oxidation Inhib' N-Butylamine Dodecylamine... Hexadecylamine Di-2-Ethyl Hexylamme...
Oyclohexylamine Di-cyclohexylamine Paraphenetidina Aniline Amino bicyclohexyl l Rust above oil level. 1 Rust below oil level.
V mono and di-phosphoric acid esters of the several aliphatic alcohols from octyl to hexadecyl alcohol may be used, mixtures of these are generally more readily available commercially. Such mixtures are intended to be included within the scope of the term alkyl acid phosphate as used in the claims and the word phosphate is intended to include a single phosphate or a plurality of the same unless otherwise specifically indicated.
This application is a continuation-in-part of my copending application Serial Number 130,345, filed November 30, 1949, now Patent No. 2,605,226.
I claim:
1. As a new chemical compound, suitable for use as a rust inhibiting additive for mineral oils, the addition product of amino bicyclohexyl and alkyl acid phosphate containing from 8 to 16. carbon atoms in each alkyl group.
2. The compound of claim 1 wherein the amino bicyclohexyl is ortho amino bicyclohexyl.
3. The compound of claim 1 wherein the amino bicyclohexyl is meta amino bicyc1ohexy1.
4. The compound of claim 1 wherein the alkyl. acid phosphate is a mixture of phosphoric acidesters of fatty alcohols of 8 to 12 carbon atoms derived from cocoanut and palm oils.
5. A process for the manufacture of the addition product of amino bicyclohexyl and alkyl acid phosphate which comprises: heating amino bicyclohexyl to a temperature between 212 and 270 F., then cooling and subsequently reactin said amine with alkyl acid phosphate having from 8 to 16 carbon atoms per alkyi group while maintaining the reaction temperature between 100 and 200 F.
SAMUEL CLYDE VAUGHN.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,285,854 Downing June 9, 1942 10 2,371,853 Smith Mar. 20, 1945 2,413,852 Turner Jan. 7, 1947 2,516,914 Revukas Aug. 1, 1950 2,574,955 Bishop Nov. 13, 1951
Claims (1)
1. AS A NEW CHEMICAL COMPOUND, SUITABLE FOR USE AS A RUST INHIBITING ADDITIVE FOR MINERAL OILS, THE ADDITION PRODUCT OF AMINO BICYCLOHEXYL AND ALKYL ACID PHOSPHATE CONTAINING FROM 8 TO 16 CARBON ATOMS IN EACH ALKYL GROUP.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US245429A US2656375A (en) | 1951-09-06 | 1951-09-06 | Amino bicyclohexyl-alkyl acid phosphate reaction product |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US245429A US2656375A (en) | 1951-09-06 | 1951-09-06 | Amino bicyclohexyl-alkyl acid phosphate reaction product |
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Publication Number | Publication Date |
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US2656375A true US2656375A (en) | 1953-10-20 |
Family
ID=22926614
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US245429A Expired - Lifetime US2656375A (en) | 1951-09-06 | 1951-09-06 | Amino bicyclohexyl-alkyl acid phosphate reaction product |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2728646A (en) * | 1952-04-01 | 1955-12-27 | Tide Water Associated Oil Comp | Gasoline containing corrosion inhibitor |
DE1057121B (en) * | 1957-03-08 | 1959-05-14 | Hoechst Ag | Process for the preparation of piperazine carboxylic acid esters effective against schistosomiasis |
US3063820A (en) * | 1959-05-18 | 1962-11-13 | Universal Oil Prod Co | Stabilization of hydrocarbons |
US3188340A (en) * | 1961-12-08 | 1965-06-08 | Du Pont | Polyfluoro alkanamidoalkyl phosphates |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2285854A (en) * | 1934-02-23 | 1942-06-09 | Du Pont | Lubrication |
US2371853A (en) * | 1943-09-27 | 1945-03-20 | Gulf Oil Corp | Mineral oil composition |
US2413852A (en) * | 1944-08-30 | 1947-01-07 | Atlantie Refining Company | Rust-inhibiting lubricant |
US2516914A (en) * | 1947-03-21 | 1950-08-01 | Tide Water Associated Oil Comp | Emulsification-inhibited polyacrylate-containing oil compositions |
US2574955A (en) * | 1948-07-14 | 1951-11-13 | Tide Water Associated Oil Comp | Esterified alkylolamine salts of acid esters of phosphorus acids |
-
1951
- 1951-09-06 US US245429A patent/US2656375A/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2285854A (en) * | 1934-02-23 | 1942-06-09 | Du Pont | Lubrication |
US2371853A (en) * | 1943-09-27 | 1945-03-20 | Gulf Oil Corp | Mineral oil composition |
US2413852A (en) * | 1944-08-30 | 1947-01-07 | Atlantie Refining Company | Rust-inhibiting lubricant |
US2516914A (en) * | 1947-03-21 | 1950-08-01 | Tide Water Associated Oil Comp | Emulsification-inhibited polyacrylate-containing oil compositions |
US2574955A (en) * | 1948-07-14 | 1951-11-13 | Tide Water Associated Oil Comp | Esterified alkylolamine salts of acid esters of phosphorus acids |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2728646A (en) * | 1952-04-01 | 1955-12-27 | Tide Water Associated Oil Comp | Gasoline containing corrosion inhibitor |
DE1057121B (en) * | 1957-03-08 | 1959-05-14 | Hoechst Ag | Process for the preparation of piperazine carboxylic acid esters effective against schistosomiasis |
US3063820A (en) * | 1959-05-18 | 1962-11-13 | Universal Oil Prod Co | Stabilization of hydrocarbons |
US3188340A (en) * | 1961-12-08 | 1965-06-08 | Du Pont | Polyfluoro alkanamidoalkyl phosphates |
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