US3706668A - Polyphenyl ether lubricating compositions - Google Patents
Polyphenyl ether lubricating compositions Download PDFInfo
- Publication number
- US3706668A US3706668A US148124A US3706668DA US3706668A US 3706668 A US3706668 A US 3706668A US 148124 A US148124 A US 148124A US 3706668D A US3706668D A US 3706668DA US 3706668 A US3706668 A US 3706668A
- Authority
- US
- United States
- Prior art keywords
- acid
- phenoxyphenylphosphinic
- polyphenyl ether
- composition
- benzene
- 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
- 239000000203 mixture Substances 0.000 title abstract description 38
- 229920013636 polyphenyl ether polymer Polymers 0.000 title abstract description 23
- 230000001050 lubricating effect Effects 0.000 title description 7
- 239000002253 acid Substances 0.000 abstract description 3
- 150000007513 acids Chemical class 0.000 abstract 1
- -1 3,3-bisphenoxy biphenyl Chemical group 0.000 description 39
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- MSVORCUEJCHPKS-UHFFFAOYSA-N phenoxy(phenyl)phosphinic acid Chemical class C=1C=CC=CC=1P(=O)(O)OC1=CC=CC=C1 MSVORCUEJCHPKS-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- UYWYRBHBVOLSCA-UHFFFAOYSA-N O(C1=CC=CC=C1)C1=CC=C(C=C1)P(O)=O Chemical compound O(C1=CC=CC=C1)C1=CC=C(C=C1)P(O)=O UYWYRBHBVOLSCA-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 125000001188 haloalkyl group Chemical group 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- KYSKNYFGWVBAOD-UHFFFAOYSA-N 1,3-bis(4-phenoxyphenoxy)benzene Chemical compound C=1C=C(OC=2C=C(OC=3C=CC(OC=4C=CC=CC=4)=CC=3)C=CC=2)C=CC=1OC1=CC=CC=C1 KYSKNYFGWVBAOD-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000010533 azeotropic distillation Methods 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000004508 fractional distillation Methods 0.000 description 2
- PSFDQSOCUJVVGF-UHFFFAOYSA-N harman Chemical compound C12=CC=CC=C2NC2=C1C=CN=C2C PSFDQSOCUJVVGF-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- IZJSTVXIRSFCBX-UHFFFAOYSA-N 1,2-bis(3-phenoxyphenoxy)benzene Chemical compound C=1C=CC(OC=2C(=CC=CC=2)OC=2C=C(OC=3C=CC=CC=3)C=CC=2)=CC=1OC1=CC=CC=C1 IZJSTVXIRSFCBX-UHFFFAOYSA-N 0.000 description 1
- KOKDSALTQSQPDH-UHFFFAOYSA-N 1,3-bis(3-phenoxyphenoxy)benzene Chemical compound C=1C=CC(OC=2C=C(OC=3C=C(OC=4C=CC=CC=4)C=CC=3)C=CC=2)=CC=1OC1=CC=CC=C1 KOKDSALTQSQPDH-UHFFFAOYSA-N 0.000 description 1
- WVOCXQKXUBYPNN-UHFFFAOYSA-N 1,4-diphenoxy-2-(3-phenoxyphenoxy)benzene Chemical compound C=1C=CC(OC=2C(=CC=C(OC=3C=CC=CC=3)C=2)OC=2C=CC=CC=2)=CC=1OC1=CC=CC=C1 WVOCXQKXUBYPNN-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 229910001315 Tool steel Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 125000005998 bromoethyl group Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- NSMYKMIEFQWHIL-UHFFFAOYSA-N dichloro-(4-phenoxyphenyl)phosphane Chemical compound C1=CC(P(Cl)Cl)=CC=C1OC1=CC=CC=C1 NSMYKMIEFQWHIL-UHFFFAOYSA-N 0.000 description 1
- 125000006003 dichloroethyl group Chemical group 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 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
- 238000010828 elution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 125000005843 halogen group Chemical group 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
- GBHRVZIGDIUCJB-UHFFFAOYSA-N hydrogenphosphite Chemical compound OP([O-])[O-] GBHRVZIGDIUCJB-UHFFFAOYSA-N 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- MLCHBQKMVKNBOV-UHFFFAOYSA-N phenylphosphinic acid Chemical compound OP(=O)C1=CC=CC=C1 MLCHBQKMVKNBOV-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M3/00—Liquid compositions essentially based on lubricating components other than mineral lubricating oils or fatty oils and their use as lubricants; Use as lubricants of single liquid substances
-
- 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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
-
- 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
- C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
- C10M2223/061—Metal salts
Definitions
- This invention relates to improved lubricating compositions comprising polyphenyl ethers and mixtures thereof containing from 3 to 8 aromatic groups and a phenoxyphenylphosphinic acid as a lubricating additive.
- Polyphenyl ethers have found wide application as functional fluids in view of their excellent thermal stability and lubricity. For example they have been found to be valuable as hydraulic fluids and as lubricants in motor operation, particularly in jet engines.
- An object of the present invention is to provide base stock compositions employing polyphenyl ethers or mixtures thereof that exhibit improved lubricating properties.
- compositions comprising a major amount of a polyphenyl ether base stock and a lubricating additive amount of a phenoxyphenylphosphinic acid, have unusual ability to lubricate under high loads at high temperatures.
- polyphenyl ether base stocks Any of the well known polyphenyl ether base stocks can be used in accordance with this invention. However, the polyphenyl ether base stocks represented by a member selected from the following formulae are preferred.
- polyphenyl ethers in which the nonterminal phenylene rings are linked through oxygen atoms in the meta and/ or parapositions, have been found to be particularly suitable.
- An example of such polyphenyl ether compositions are those containing, in percent by weight, from about 0 to 6% of o-bis(m-phenoxyphenoxy)benzene (1), about 40 to of m-bis(m-phenoxyphenoxy)benzene (2), about 0 to 40% of m-[(m-phenoxyphenoxy) (p-phenoxyphenoxy)]benzene (3), about 0 to 12% of pbis(m-phenoxyphenoxy)benzene (4) about 0 to 10% of p- [p-phenoxyphenoxy) (m-phenoxyphenoxy) ]benzene (5), and about 0 to 6% of m-bis(p-phenoxyphenoxy)benzene (6).
- Typical compositions of such mixtures are listed below. The number of parentheses refers to the compound mentioned above
- R and R are alkyl of not more than 4 carbon atoms, haloalkyl of not more than 4 carbon atoms and 3 halogen (Cl, Br and F) atoms, halogen (Cl, Br and F) hydroxyl or phenyl, and n and a are integers from 0 to 3.
- R and R in the above formulae include alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and t-butyl and haloalkyl such as chloromethyl, brornomethyl, chloroethyl, bromoethyl, trichloromethyl, tribromomethyl, dichloroethyl, chloro-npropyl, bromo-n-propyl, bromo-n-butyl, bromo-tert-butyl, 1,3,3-trich1orobutyl and 1,3,3-tribromobutyl.
- alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and t-butyl and haloalkyl
- haloalkyl such as chloromethyl, brornomethyl, chloroethyl, bromoe
- Phenoxyphenylphosphinic acids represented by the above formula include, for example,
- p-phenoxyphenylphosphinic acid o-phenoxyphenylphosphinic acid, p-(p-methylphenoxy)phenylphosphinic acid, o- (p-methylphenoxy)phenylphosphinic acid, p-(o-methylphenoxy)phenylphosphinic acid, p- (p-ethylphenoxy) phenylphosphinic acid, p-(o-ethylphenoxy) phenylphosphinic acid, o-(o-ethylphenoxy)phenylphosphinic acid, p-(p-butylphenoxy)phenylphosphinic acid, p- (p-chlorophenoxy)phenylphosphinic acid, o-(m-chlorophenoxy)phenylphosphinic acid, p-(p-phenylphenoxy)phenylphosphinic acid, -(p-phenylphenoxy)phenylphosphinic
- the improvement in lubricity characteristics achieved by the addition of the phenoxyphenylphosphinic acids to the polyphenyl ether base fluid is unusual and surprising.
- the compositions are particularly useful for steel on steel lubrimtion.
- compositions of this invention contain a major amount of the polyphenyl ether base stock, i.e., at least 50% by weight of the total composition comprises a polyphenyl ether. It is preferred that at least 60% by weight of the composition be a polyphenyl ether base stock and even more preferred that at least 85% by weight of the total composition comprise a polyphenyl ether.
- compositions of this invention can also contain from 0.01 to by weight of the total composition of a dialkyl hydrogen phosphite extreme pressure additive.
- the dialkyl hydrogen phosphites useful are those wherein the alkyl groups contain from 1 to 12 carbon atoms. These alkyl groups are, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, hexyl, decyl isodecyl, dodecyl and the like.
- phenoxyphenylphosphinic acids useful in this invention are prepared by interaction of a phosphine of the formula wherein R, R n and a are as defined above with ethyl alcohol and water.
- the interaction is carried out in the absence of a solvent by heating the admixture of the three components at temperatures up to and including reflux temperature. Pressure is not critical and subatmospheric, atmospheric and superatmospheric pressures can be employed. It is generally preferred to slowly add the phosphine to the ethyl alcohol and then to add the water to the admixture of phosphine and ethyl alcohol prior to heating. After reaction is complete, generally a period not exceeding more than ten or fifteen minutes, the excess ethyl alcohol and water are removed by azeotropic distillation with an azeotroping agent such as benzene.
- an azeotroping agent such as benzene.
- the separation of the desired phosphinic acid from the azeotroping agent is readily accomplished by conventional means well known to the art. For example, distillation, fractional distillation under reduced pressure, selective extraction, fractional distillation using a carrier gas, film distillation, evaporation, elution, or any suitable combination of these methods.
- Dichlorophenoxyphenylphosphines can be prepared by Friedel-Craft condensation of diphenyl ethers with phosphorus trichloride in accordance with the procedure set forth in Organic Synthesis, 31, p. 88 (1951).
- EXAMPLE 1 This example describes the preparation of p-phenoxyphenylphosphinic acid.
- One part of dichloro-p-phenoxyphenylphosphine (B.P. 138-143 C./0.5 mm. Hg) is slowly added to five parts of absolute ethyl alcohol in a suitable vessel and then two parts of water are added to the alcohol phosphine admixture with continuous stirring. The resulting mixture is heated at reflux for about five minutes.
- Evaporation of alcohol and water provides an oily substance. Residual alcohol and water are removed from the oily substance by azeotropic distillation using benzene as the azeotroping agent. The benzene is removed from the acid by evaporation producing an oil which slowly crystallizes.
- the crystals are dried and subjected to recrystallization from benzene and from an admixture of 70% benzene and 30% petroleum ether (B.P. 30-75 C.).
- the product p-phenoxyphenylphosphinic acid has a melting point of 96.5-98 C. and is confirmed by N.M.R.
- a polyphenylether lubricant composition is prepared by combining p-phenoxyphenylphosphinic acid (0.10 gram) with 100 grams of a polyphenyl ether of the following composition:
- the speed of rotation is very low, namely one r.p.m. This equals 0.88 inch/minute. This is done for two reasons. It insures boundary conditions, i.e., metal to metal contact. It also eliminates metal skin temperature flashes which can occur at high speeds. Thus the bulk oil temperature is equivalent to the metal surface temperature. Under these conditions wear is negligible and friction is used to follow lubrication. After covering the ball and disc with the test oil, the initial friction is recorded. The test sample is then heated at 700 F. with continuous recording of the friction. This gives a boundary frictiontemperature profile for the experimental fiuid over this temperature range.
- the p-phenoxyphenylphosphinic acid/polyphenyl ether composition of this example was tested by this procedure on MS tool steel.
- the base stock was also tested for control purposes.
- the measured coefficient of friction of the composition of this example was substantially lower than the measured coeflficient of friction for the base fluid over the temperature range from 300 F. to 700 F. and particularly from 350 F. to 430 F. and from 500 F. and 700 F.
- Composition comprising a major amount of a polyphenyl ether and from about 0.01 to about 0.5% by weight of a phenoxyphenylphosphinic acid of the formula wherein R and R are alkyl of not more than 4 carbon atoms, haloalkyl of not more than 4 carbon atoms and 3 halogen atoms, halogen, hydroxyl or phenyl and n and a are integers from 0 to 3. 2. Composition of claim 1 wherein the phenoxyphenylphosphinic acid is present in amounts of from about 0.05 to about 0.2% by weight.
- composition of claim 1 wherein the phenoxyphenylphosphinic acid is p-phenoxyphenylphosphinic acid.
- composition of claim 1 wherein the phenoxyphenylphosphinic acid is o-phenoxyphenylphosphinic acid.
- composition of claim 1 wherein the phenoxyphenylphosphinic acid is m-phenoxyphenylphosphinic acid.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Lubricants (AREA)
Abstract
COMPOSITION COMPRISING POLYPHENYL ETHERS OR MIXTURES THEREOF AND PHENOXYPHENYLPHOSPHINIC ACIDS EXHIBIT IMPROVED LURBICATING PROPERTIES OVER WIDE TEMPERATURE RANGES.
Description
United States Patent Ofice 3,706,668 Patented Dec. 19, 1972 ABSTRACT OF THE DISCLOSURE Composition comprising polyphenyl ethers or mixtures thereof and phenoxyphenylphosphinic acids exhibit improved lurbicating properties over wide temperature ranges.
This invention relates to improved lubricating compositions comprising polyphenyl ethers and mixtures thereof containing from 3 to 8 aromatic groups and a phenoxyphenylphosphinic acid as a lubricating additive.
Polyphenyl ethers have found wide application as functional fluids in view of their excellent thermal stability and lubricity. For example they have been found to be valuable as hydraulic fluids and as lubricants in motor operation, particularly in jet engines.
Development of synthetic base stocks such as the polyphenyl ether has provided lubricant fluids which are useful at elevated temperature such as 400 to 500 F. It is known that one of the aspects in Which the polyphenyl ether base stocks are considered deficient is in their lubricating characteristics. These lubricating characteristics include the load-carrying abilities and wear properties, especially under conditions of high pressures and temperatures reached in the advance design aircraft engines. Thus there is a demand for polyphenyl ethers having improved lubricity properties.
An object of the present invention is to provide base stock compositions employing polyphenyl ethers or mixtures thereof that exhibit improved lubricating properties.
These and other objects will become evident upon consideration of the following specification and example.
It has now been found that compositions comprising a major amount of a polyphenyl ether base stock and a lubricating additive amount of a phenoxyphenylphosphinic acid, have unusual ability to lubricate under high loads at high temperatures.
Any of the well known polyphenyl ether base stocks can be used in accordance with this invention. However, the polyphenyl ether base stocks represented by a member selected from the following formulae are preferred.
such as 3,3-bisphenoxy biphenyl,
where m is 2, 3, or 4 such as (III) such as 1,3,4-triphenoxybenezne,
(IV) and mixtures thereof.
Mixtures of polyphenyl ethers in which the nonterminal phenylene rings are linked through oxygen atoms in the meta and/ or parapositions, have been found to be particularly suitable. An example of such polyphenyl ether compositions are those containing, in percent by weight, from about 0 to 6% of o-bis(m-phenoxyphenoxy)benzene (1), about 40 to of m-bis(m-phenoxyphenoxy)benzene (2), about 0 to 40% of m-[(m-phenoxyphenoxy) (p-phenoxyphenoxy)]benzene (3), about 0 to 12% of pbis(m-phenoxyphenoxy)benzene (4) about 0 to 10% of p- [p-phenoxyphenoxy) (m-phenoxyphenoxy) ]benzene (5), and about 0 to 6% of m-bis(p-phenoxyphenoxy)benzene (6). Typical compositions of such mixtures are listed below. The number of parentheses refers to the compound mentioned above having the same number thereafter.
Mixtures, percent by weight of components A B C D Component:
wherein R and R are alkyl of not more than 4 carbon atoms, haloalkyl of not more than 4 carbon atoms and 3 halogen (Cl, Br and F) atoms, halogen (Cl, Br and F) hydroxyl or phenyl, and n and a are integers from 0 to 3.
Representative groups for R and R in the above formulae include alkyl such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl and t-butyl and haloalkyl such as chloromethyl, brornomethyl, chloroethyl, bromoethyl, trichloromethyl, tribromomethyl, dichloroethyl, chloro-npropyl, bromo-n-propyl, bromo-n-butyl, bromo-tert-butyl, 1,3,3-trich1orobutyl and 1,3,3-tribromobutyl.
Phenoxyphenylphosphinic acids represented by the above formula include, for example,
p-phenoxyphenylphosphinic acid, o-phenoxyphenylphosphinic acid, p-(p-methylphenoxy)phenylphosphinic acid, o- (p-methylphenoxy)phenylphosphinic acid, p-(o-methylphenoxy)phenylphosphinic acid, p- (p-ethylphenoxy) phenylphosphinic acid, p-(o-ethylphenoxy) phenylphosphinic acid, o-(o-ethylphenoxy)phenylphosphinic acid, p-(p-butylphenoxy)phenylphosphinic acid, p- (p-chlorophenoxy)phenylphosphinic acid, o-(m-chlorophenoxy)phenylphosphinic acid, p-(p-phenylphenoxy)phenylphosphinic acid, -(p-phenylphenoxy)phenylphosphinic acid, p-(o-hydroxyphenoxy)phenylphosphinic acid, p-(m-bromophenoxy)phenylphosphinic acid, p- (p-hydroxyphenyl)phenylphosphinic acid, o-(m-phenylphenoxy)phenylphosphinic acid, o-(p-methylphenoxy)m-methylphenylphosphinic acid, o- (p-methylphenoxy) -m-chloromethylphenylphosphinic acid, p-(p-methylphenoxy)-m-trifluoromethylphenylphosphinic acid, p-(o-butylphenoxy)-o-trifluoromethylphenylphosphinic acid, m-(o-phenylphenoxy)-p-methylphenylphosphinic acid, m-(o-methylphenoxy)-o-butylphenylphosphinic acid, m-(o-chloromethylphenoxy)-o-methylphenylphosphinic acid, 0-(m-methylphenoxy)-p-trifiuoromethylphenylphosphinic acid, o- (m-hydroxyphenoxy)-p-hydroxyphenylphosphinic acid, o-(m-phenylphenoxy)-m-chloromethylphenylphosphinic acid, p-(m-phenylphenoxy)-m-hydroxyphenylphosphinic acid.
The improvement in lubricity characteristics achieved by the addition of the phenoxyphenylphosphinic acids to the polyphenyl ether base fluid is unusual and surprising. The compositions are particularly useful for steel on steel lubrimtion.
The compositions of this invention contain a major amount of the polyphenyl ether base stock, i.e., at least 50% by weight of the total composition comprises a polyphenyl ether. It is preferred that at least 60% by weight of the composition be a polyphenyl ether base stock and even more preferred that at least 85% by weight of the total composition comprise a polyphenyl ether.
The compositions of this invention can also contain from 0.01 to by weight of the total composition of a dialkyl hydrogen phosphite extreme pressure additive. The dialkyl hydrogen phosphites useful are those wherein the alkyl groups contain from 1 to 12 carbon atoms. These alkyl groups are, for example, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, t-butyl, hexyl, decyl isodecyl, dodecyl and the like.
The phenoxyphenylphosphinic acids useful in this invention are prepared by interaction of a phosphine of the formula wherein R, R n and a are as defined above with ethyl alcohol and water.
The interaction is carried out in the absence of a solvent by heating the admixture of the three components at temperatures up to and including reflux temperature. Pressure is not critical and subatmospheric, atmospheric and superatmospheric pressures can be employed. It is generally preferred to slowly add the phosphine to the ethyl alcohol and then to add the water to the admixture of phosphine and ethyl alcohol prior to heating. After reaction is complete, generally a period not exceeding more than ten or fifteen minutes, the excess ethyl alcohol and water are removed by azeotropic distillation with an azeotroping agent such as benzene.
The separation of the desired phosphinic acid from the azeotroping agent is readily accomplished by conventional means well known to the art. For example, distillation, fractional distillation under reduced pressure, selective extraction, fractional distillation using a carrier gas, film distillation, evaporation, elution, or any suitable combination of these methods.
Dichlorophenoxyphenylphosphines can be prepared by Friedel-Craft condensation of diphenyl ethers with phosphorus trichloride in accordance with the procedure set forth in Organic Synthesis, 31, p. 88 (1951).
The following examples serve to further illustrate the invention. All parts are parts by weight unless otherwise expressly set forth.
EXAMPLE 1 This example describes the preparation of p-phenoxyphenylphosphinic acid. One part of dichloro-p-phenoxyphenylphosphine (B.P. 138-143 C./0.5 mm. Hg) is slowly added to five parts of absolute ethyl alcohol in a suitable vessel and then two parts of water are added to the alcohol phosphine admixture with continuous stirring. The resulting mixture is heated at reflux for about five minutes. Evaporation of alcohol and water provides an oily substance. Residual alcohol and water are removed from the oily substance by azeotropic distillation using benzene as the azeotroping agent. The benzene is removed from the acid by evaporation producing an oil which slowly crystallizes. The crystals are dried and subjected to recrystallization from benzene and from an admixture of 70% benzene and 30% petroleum ether (B.P. 30-75 C.). The product p-phenoxyphenylphosphinic acid has a melting point of 96.5-98 C. and is confirmed by N.M.R.
EXAMPLE 2 A polyphenylether lubricant composition is prepared by combining p-phenoxyphenylphosphinic acid (0.10 gram) with 100 grams of a polyphenyl ether of the following composition:
Percent m-Bis(mphenoxyphenoxy)benzene 65.0 m-(m-Phenoxyphenoxy)phenyl-p-phenoxyphenylether m-Bis(p-phenoxyphenoxy)benzene 3 kg. load 1 r.p.m. Room temperature to 700 F.
The speed of rotation is very low, namely one r.p.m. This equals 0.88 inch/minute. This is done for two reasons. It insures boundary conditions, i.e., metal to metal contact. It also eliminates metal skin temperature flashes which can occur at high speeds. Thus the bulk oil temperature is equivalent to the metal surface temperature. Under these conditions wear is negligible and friction is used to follow lubrication. After covering the ball and disc with the test oil, the initial friction is recorded. The test sample is then heated at 700 F. with continuous recording of the friction. This gives a boundary frictiontemperature profile for the experimental fiuid over this temperature range.
The p-phenoxyphenylphosphinic acid/polyphenyl ether composition of this example was tested by this procedure on MS tool steel. The base stock was also tested for control purposes. The measured coefficient of friction of the composition of this example was substantially lower than the measured coeflficient of friction for the base fluid over the temperature range from 300 F. to 700 F. and particularly from 350 F. to 430 F. and from 500 F. and 700 F.
I claim:
1. Composition comprising a major amount of a polyphenyl ether and from about 0.01 to about 0.5% by weight of a phenoxyphenylphosphinic acid of the formula wherein R and R are alkyl of not more than 4 carbon atoms, haloalkyl of not more than 4 carbon atoms and 3 halogen atoms, halogen, hydroxyl or phenyl and n and a are integers from 0 to 3. 2. Composition of claim 1 wherein the phenoxyphenylphosphinic acid is present in amounts of from about 0.05 to about 0.2% by weight.
3. Composition of claim 1 wherein the phenoxyphenylphosphinic acid is p-phenoxyphenylphosphinic acid.
4. Composition of claim 1 wherein the phenoxyphenylphosphinic acid is o-phenoxyphenylphosphinic acid.
5. Composition of claim 1 wherein the phenoxyphenylphosphinic acid is m-phenoxyphenylphosphinic acid.
6. Composition of claim 1 wherein R and R are alkyl and n and a are one.
7. Composition of claim 1 wherein R is alkyl, n is one and a is zero.
8. Composition of claim 1 wherein R is phenyl, n is one, and a is zero.
9. Composition of claim 1 wherein R is hydroxyl, n is one and a is zero.
10. Composition of claim 5 wherein R and R are methyl.
References Cited UNITED STATES PATENTS 2,614,990 10/1952 Harman et a1 252-499 2,913,415 11/1959 Schmitz 252-49.8 X
FOREIGN PATENTS 606,672 10/1960 Canada 25249.9'
851,651 10/1960 Great Britain 252-52 R DANIEL E. WYMAN, Primary Examiner W. H. CANNON, Assistant Examiner US. Cl. X.R.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14812471A | 1971-05-28 | 1971-05-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3706668A true US3706668A (en) | 1972-12-19 |
Family
ID=22524388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US148124A Expired - Lifetime US3706668A (en) | 1971-05-28 | 1971-05-28 | Polyphenyl ether lubricating compositions |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3706668A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5196130A (en) * | 1991-12-09 | 1993-03-23 | The United States Of America As Represented By The Secretary Of The Air Force | Lubricity additive for high-temperature gas turbine engine oils |
| EP0612837A1 (en) * | 1993-01-06 | 1994-08-31 | Akzo Nobel N.V. | Polyphenylene ether lubricant containing hydrocarbyl bis(dihydrocarbylphosphate) compound |
| JP3213312B2 (en) | 1991-12-25 | 2001-10-02 | ソリュテイア・インコーポレイテッド | Method for producing antioxidant fluid composition |
-
1971
- 1971-05-28 US US148124A patent/US3706668A/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5196130A (en) * | 1991-12-09 | 1993-03-23 | The United States Of America As Represented By The Secretary Of The Air Force | Lubricity additive for high-temperature gas turbine engine oils |
| JP3213312B2 (en) | 1991-12-25 | 2001-10-02 | ソリュテイア・インコーポレイテッド | Method for producing antioxidant fluid composition |
| EP0612837A1 (en) * | 1993-01-06 | 1994-08-31 | Akzo Nobel N.V. | Polyphenylene ether lubricant containing hydrocarbyl bis(dihydrocarbylphosphate) compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4087386A (en) | Triaryl phosphate ester functional fluids | |
| US3274107A (en) | Lubricant composition containing a sulfide | |
| US3182021A (en) | Lubricants containing phosphorus thioic derivatives | |
| CA1065872A (en) | Organophosphorous derivatives of benzotriazole as load-carrying additives | |
| US2274291A (en) | Compounded mineral oil | |
| US3706668A (en) | Polyphenyl ether lubricating compositions | |
| US3714043A (en) | Polyphenyl thioether lubricating compositions | |
| US2614990A (en) | Lubricating composition of matter | |
| US2293445A (en) | Lubricant with high temperature stability | |
| US3704277A (en) | Polyphenyl ether lubricating compositions | |
| US3843532A (en) | Polyphenyl thioether lubricating compositions | |
| US2820766A (en) | Lubricating compositions | |
| US3481872A (en) | Degradation resistant and non-corrosive high-temperature lubricant formulation | |
| US3071549A (en) | Preservative-type functional fluids | |
| US3778472A (en) | Phenoxyphenylphosphinic acids and improved polyphenyl thioether lubricating compositions | |
| US2913415A (en) | Method of inhibiting squawking in mineral oil transmission fluids | |
| US2188943A (en) | Lubricant and method of producing same | |
| KR20020092976A (en) | Multipurpose lubricant based on phosphorus and sulphur compounds | |
| US3423469A (en) | Polyphenyl ether compositions | |
| US4348291A (en) | Novel phosphoramides, lubricating compositions and method of improving wear and extreme pressure characteristics of lubricating oil | |
| US3677944A (en) | Polyphenyl thioether lubricating compositions | |
| US3012057A (en) | Synthetic lubricants and their preparation | |
| US3413225A (en) | Functional fluid containing azo benzene derivatives as antioxidants | |
| US3490738A (en) | Lubricant composition containing a tin compound | |
| US3536738A (en) | Bis(trimethylolpropane diallyl ether) dilinoleate and its phosphonates and lubricant compositions |