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
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/22—Tin compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
  • C08G79/12—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing tin
• • 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
  • C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
  • C10M2227/08—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions having metal-to-carbon bonds
  • C10M2227/083—Sn compounds
• • 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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/08—Resistance to extreme temperature
• • 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
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/32—Light or X-ray resistance
• • 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
  • C10N2040/08—Hydraulic fluids, e.g. brake-fluids
• • 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
  • C10N2040/12—Gas-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
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/12—Gas-turbines
  • C10N2040/13—Aircraft 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
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/25—Internal-combustion engines
• • 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
  • C10N2040/25—Internal-combustion engines
  • C10N2040/251—Alcohol fueled engines
• • 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
  • C10N2040/25—Internal-combustion engines
  • C10N2040/255—Gasoline engines
• • 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
  • C10N2040/25—Internal-combustion engines
  • C10N2040/255—Gasoline engines
  • C10N2040/28—Rotary engines
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S376/00—Induced nuclear reactions: processes, systems, and elements
  • Y10S376/90—Particular material or material shapes for fission reactors
  • Y10S376/904—Moderator, reflector, or coolant materials
  • Y10S376/905—Organic

Definitions

• This invention relates to liquid fluids of high thermal stability and more particularly provides functional fluids comprising polyphenyl ethers and certain organic compounds of tin as adjuvants therefor.
• the polyphenyl ethers are known compounds which have found wide application as functional fluids owing to their very good thermal stability, resistance to foam, and lubricity. For example, they have been found to be valuable as hydraulic fluids, as heat-exchange media, as atomic reactor coolants, as diffusion pump fluids, as lubricants in motor operation generally, and particularly as jet engine lubricants.
• petroleum lubricants generally comprise, in addition to the petroleum base stock, additives or adjuvants which impart specifically desired properties to the base stock, e.g., rust-inhibitors, anitioxidants, extreme pressure-resisting agent, lubricity improvers, detersives, etc.
• additives proposed heretofore have been designed to accommodate the requirements of petroleum base stocks for lubrication in conventional equipment such as internal combustion engines of the automotive type, diesel engines and the like.
• One feature in common with respect to these various applications was that the temperature of use was not excessive, i.e., it may vary from about 40 F. to 400 F.
• the polyphenyl ethers possess extremely good thermal stability, at temperatures of, say, over 550 F., they tend to deteriorate, not because of a decomposition reaction, but because at the higher temperatures they become quite readily oxidizable.
• the lubricity of the polyphenyl ethers is thereby impaired, since the oxidation products do not possess lubricating properties; moreover, the change in viscosity which is a consequence of the oxidation not only makes for inetficiency, but also may clog up the moving parts of the mechanism which the lubricant was originally intended to protect.
• the polyphenyl ethers are to be used at the higher temperatures under conditions requiring exposure to air, it is necessary 3,290,247 Patented Dec. 6, 1966 to inhibit oxidation phenomena which the higher temperatures favor.
• polyphenyl ethers like conventional petroelum lubricants, are also somewhat deficient with respect to lubricity, anti-wear and extreme pressure-resisting properties, e.g., breakdown of lubricant film occurs under some conditions of use, particularly at the extreme pressures encountered in gear lubrication.
• conventional lubricity, anti-wear and extreme pressure-resisting (E.P.) additives are generally ineifective with the polyphenyl ethers and do not withstand the very high temperatures at which the high thermal stability of the ethers could make them of most use.
• W V 7 Accordingly, an object of the present invention is the provision of improved polyphenyl ether fluid compositions.
• Another object of the invention is the provision of polyphenyl ether compositions having improved antioxidant properties. Still another object of the invention is the provision of polyphenyl ether compositions having improved lubricity. A further object is the provision of polyphenyl ether compositions having improved anti-wear properties. Still a further object is the provision of polyphenyl ether compositions having improved extreme pressure-resisting properties. A most important object of the invention is the provision of polyphenyl ether compositions which possess an improved resistance to oxidation at temperatures of over 560 F.
• Particularly valuable are compounds selected from the class consisting of those having the formula where n is a number of from 2 to 3, m is a number of 1 to 2 and the total of m+n is 4,
• R is selected from the class consisting of alkyl radicals of from 1 to 12 carbon atoms, benzenoid hydrocarbon radicals which are free of olefinic and acetylenic unsaturation and contain from 6 to 12 carbon atoms, and aryloxyaryl radicals of from 12 to 24 carbon atoms, and such radicals carrying halogen substitution;
• R is selected from the class consisting of R, paraffinic and haloparaflinic acyl radicals of from 2 to 12 carbon atoms, the radical wherein Z denotes the necessary members to complete a saturated heterocyclic radical of from 6 to 10 members, the radicals -SnR and -ary1eneOSnR and X is a chalcogen element having an atomic weight of less than 33; and those having the formula Lil.
• Y is selected from the class consisting of arylene radicals of from 6 to 12 carbon atoms, arylenealkylenearylene radicals and alkylene-arylenealkylene radicals having from 1 to 4 carbon atoms in the alkylene radical and from 6 to 12 carbon atoms in the arylene radical
• R and X are as above defined
• y is a number denoting the degree of polymerization.
• R Sn(XR) Compounds having the formula R Sn(XR) are derivatives of tin hydroxides or thiols.
• the compounds are hydrocarbonoxytin .
• the corresponding thio compounds have the formula: R SnSR Rz t mz
• Examples of C are ben'zylthiotripropyltin, decylthiotriphenyltin, iodophenylthiotrimethyltin, heptylthiotris(ptolyloxyphenyDtin, tributylphenylthiotin and tri-pentyl-p-- biphenylylthiotin.
• Examples of D are dibutylbis(buty1 thio tin, diphenyl'bis (phenylthion )tin, diphentylbis benzylthio) tin, bis p-phenoxyphenyl) bis (p-phenoxyphenoxy) tin, etc.
• R' is an acyl radical
• the presently useful compounds are esters of parafiinic or haloparafiinic acids.
• the com pounds have the formula:
• R is selected from the class consisting of tate, tris(p-tolyl)tin 3-fluorothiopropionate, and tripentyltin thiodecanoate.
• Compounds of the Formula G include dihydrocarbontin or bis(hydrocarbonoxyhydrocarbon)tin alkanoates, e.g., diphenyltin dihexoate, dibutyltin dinonoate, bis'( 4-phenoxyphenyl)tin or dixylyltin dipropionate.
• diaryltin bis(haloalkanoates) having from 6 to 12 carbon atoms in each aryl group and from 1 to carbon atoms in each haloalkanoate group, e.g., diphenyltin bis(2-fluoropropionate), di-p-tolyltin bis(tetra'bromobutyrate), di-u-naphthyltin bis(iodoacetate), (bis pbiphenylyDt-in bis(trichloroacetate), diphenyltin bis(chlorovaler-ate) etc.
• diphenyltin bis(2-fluoropropionate) di-p-tolyltin bis(tetra'bromobutyrate), di-u-naphthyltin bis(iodoacetate), (bis pbiphenylyDt-in bis(trichloroacetate), diphenyltin bis(chlorovaler-ate) etc.
• Examples of compounds of the Formula H are diphenyltin bis(thiopropionate), di a-naphthyltin bis(thiochl0- roacetate) or dipentyltin bis'(t-hiolaurate).
• R is the nitrogenous heterocyclic radical
• the presently useful compounds have the formula Illustrative of I where X is sulfur is (Z-benzothiazolylthio)tri-b utyltin, and illustrative of I Where X is oxygen is bis(S-quinolyloxy)di-o-tolyltin.
• the presently useful compounds may also be organic tin oxides or sulfides, i.e., compounds of the formula:
• I l O O l where X is halogen, hydro is selected from the class consisting of alkyl, aryl, alkaryl and aralkyl radicals of from 1 to 12 carbon atoms and n is a number of from 1 t0 5.
• arylene group contains from 6 to 1Q carbon atoms, e.g., phenylene, biphenylylene, naphthylene, tolylylene, sylylene, etc., and R is alkyl, aryl or aryloxyaryl.
• R is aromatic hydrocarbon
• the useful compounds are derivatives of hydroquinone, catechol or resorcinol.
• antioxidants are polymeric organic tin oxides or sulfides, e.g., such as those described in the copending application of Glenn R. Wilson, Serial No. 194,642, filed of even date and now US. Patent No. 3,184,430.
• the presently useful organotin polymers consist essentially of the repeating unit:
• Y is arylene of from 6 to 12 carbon atoms or alkylenearylenealkylene where arylene has from 6 to 12 carbon atoms and alkylene has from 1 to 4 carbon atoms
• X is oxygen or sulfur
• R is an alkyl radical or a saturated benzenoid hydrocarbon radical or such a radical carrying halogen substitution or an aryloxyaryl radical.
• the number of such units in the polymeric product will vary, but will generally be from, say, to 1000.
• the polymers are oxygen and/ or sulfur ethers.
• the polymers when Y is phenylene and X is oxygen, the polymers consist of the oxygen ether unit
• a polymer of the above formula wherein R is an alkyl radical has the phenyleneoxydialkyltinoxy unit, and is readily obtained by reaction of a dihydroxybenzene, i.e., hydroquinone, catechol or resorcinol, and a dialkyltin dihalide.
• a dihydroxybenzene i.e., hydroquinone, catechol or resorcinol
• a dialkyltin dihalide Presently useful polymers of the above formula having thio linkages instead of oxygen linkages are obtained by using a dithiol instead of the dihydroxybenzene compound.
• Polymers having both oxygen and sulfur linkages are also presently useful. These are obtained by employing mercaptophenols instead of the dihydroxy compounds or the dithiols.
• the arylene group need not be the phenylene group. Instead, it may be the biphenylylene group derived, e.g., by using dihydroxybiphenyl with the diorganotin dihalide; or it may be the naphthylene group, the fluorenylene group, the acenaphthylene group, etc. Also, the bivalent aromatic nucleus may or may not carry one or more alkyl or cycloalkyl substituents, e.g., it may be the cyclopentylphenylene, the
• the polymers are derived generally from the arenebis(alkanols) or the arenebis(alkanethiols), e.g., 0-, mor p-xylene-a,et'-diol, durene-a,a'-diol, o-, mor p-benzenediethanol, o-, mor p benzenebis(ethanethiol), p xylene-m-ol-d-thiol, 1,4- naphthalenedirnethanol, 4,4'-biphenyldiethanol, etc.
• reaction of p-xylene-u,u'-diol and diphenyltin chloride gives a presently useful polymer having the repeating unit Polymers having two oxygen and/ or sulfur linkages C Ha C 2H5
• organotin compounds are generally prepared by reaction of a diorganotin dihalide or of a triorganotin trihalide with an organic compound containing at least one hydroxy, thiol, carboxy, or thiocarboxy group, with evolution of hydrogen halide.
• Others are prepared by reaction of a dihydrocarbontin oxide and hydroxy compounds or thiols with evolution of water.
• reaction may be effected by simply contacting the two reactants in the presence or absence of a solvent or diluent at ordinary or increased temperatures.
• a diluent is employed, reaction is conducted at the refiuxing temperature of the mixture in order thereby to minimize reaction time.
• catalysts are not generally necessary, reaction may sometimes be accelerated by the use of a catalytic quantity of a basic agent, e.g., an alkali metal hydroxide or a basic salt or alcoholate thereof, a quaternary ammonium compound, etc.
• catalyst is dispensed with by working with alkali metal or ammonium salts of the hydroxy compounds or thiols rather than with the free alcohols, phenols or thiols.
• alkali metal or ammonium salts of the hydroxy compounds or thiols rather than with the free alcohols, phenols or thiols.
• use of a diluent which forms an azeotrope with water is recommended.
• the organotin halogen compound and the hydroxy, thio or carboxy compound are used in stoichiometric proportions. However, an excess of either reactant may be employed, since unreacted material is readily recovered from the final product.
• the polyphenyl ethers to which this invention pertains have from 4 to 7 benzene rings and from 3 to 6 oxygen atoms. They can be represented by the structure where n is a whole number from 2 to 5.
• the preferred polyphenyl ethers are those having all their ether linkages in the meta position since the all-metal linked ethers are the best suited for many applications because of their wide liquid range and high degree of thermal stability.
• mixtures of the polyp-henyl ethers i.e., either isomeric mixtures or mixtures of homologous ethers, can also be used to obtain certain properties, e.g., lower solidification points.
• polyphenyl ethers contemplated are the bis(phenoxyphenyl) ethers, e.g., bis(m-phen-oxyphenyl) ether, the -bis(phenoxyphenoxy) benzenes, e.g., m bis(m-phenoxyphenoxy)benzene, mbis (p phenoxyphenoxy)benzene, o bis(o phenoxyphenoxy)benzene, the bis(phenoxyphenoxyphenyl) ethers, e.g., bis[m-(m-iphenoxyphenoxy)phenyl] ether, bis[p-(pphenoxyphenoxy) phenyl] ether, m [m phenoxyphenoxy) (o-phenoxyphenyl)] ether and the his (phenoxyphenoxyphenoxy)benzenes, e.g., m-bis[m-(m phenoxyphenoxy)phenoxy]benzene, p-bis[p-('m phenoxyphenoxy
• mixtures of the polyphenyl ethers can be used.
• mixtures of polyphenyl ethers in which the non-terminal phenylene rings i.e., those rings enclosed in the brackets in the above structural representation of the polyphenyl ethers contemplated
• a preferred polyphenyl ether mixture of this invention is the mixture of -.ring polyphenyl ethers where the non-terminal phenylene rings are linked through oxygen atoms in the meta and para position and composed, by weight, of about 65% m-bis(m-phenoxyphenoxylbenzene, 30% m-[(m-phenoxyphenoxy) (p-phenoxyphenoxy)]benz ene and 5% m bis(p phenoxyphenoxy)benzene.
• Such a mixture solidifies at about 10 F., whereas the three components solidify individually at temperatures above normal room temperatures.
• the aforesaid polyphenyl ethers can be obtained by the Ullmann ether synthesis which broadly relates to ether forming reactions, e.g., alkali metal phenoxides such as sodium and potassium phenoxides are reacted with aromatic halides such as bromobenzene in the presence of a copper catalyst such as metallic copper, copper hydroxides, or copper salts.
• alkali metal phenoxides such as sodium and potassium phenoxides are reacted with aromatic halides such as bromobenzene in the presence of a copper catalyst such as metallic copper, copper hydroxides, or copper salts.
• the present oxygenated organic tin compounds are combined with the fluid polyphenyl ethers to the extent of 0.1% to 10.0% by weight depending upon the nature of the tin compound and of the ether fluid and upon the 'adjuvant effect desired.
• the tin compounds generally have a beneficial effect on the polyphenyl ether in that there is obtained improvement in stability to oxidation and/or increased lubricity and/or increased resistance to wear and extreme pressure. All of these benefits do not necessarily result from the use of one additive, although a number of the tin compounds do confer a plurality of such effects when employed with the ethers within the above-stated range of concentration.
• Whether or not a desired adjuvant effect is obtained is readily determined by use of conventional testing procedures known to those skilled in the :art.
• the effectiveness of the present tin compound additive is also not the same over the entire range of concentration; for example, while it has been noted that in most cases the ability of the agent with respect to anti-wear and extreme pressure lubrication improves markedly -as the concentration is increased, the reverse may be true insofar as antioxidant effect is conoerned, lower amounts of the additive often resulting in a greater degree of stability to oxidation at the high temperatures than that attained by use of the greater amounts of the same additive.
• the anti-wear and extreme pressure lubrication characwheel The anti-wear and extreme pressure lubrication characwheel.
• the 4-ball Wear Tester was used to evaluate the ER and anti-wear characteristics of the lubricant additives of the present invention. It consists of an equilateral tetrahedron formed by four stainless steel balls, with the three lower balls immovably clamped in a ball holder. The fourth or upper ball is rotated about a vertical axis in contact with the three lower stationary balls under prescribed conditions of load, speed, temperature, and time in accordance with the following schedule.
• a modified cup and heater assembly is used to evaluate lubricants at 400 F. and higher temperatures and provisions have been provided which permit testing under an inert atmosphere. See The Study of Lubrication Using the Four-Ball Type Machine, R. G. Larsen, Lubrication Engineering, vol. 1, pp. 35-43, 59, August 1945.
• the Four-Ball E. P. Tester consists of four balls of stainless steel arranged in the form of an equilateral tetrahedron.
• the basic elements are three lower balls held immovably in a clamp to form a cradle in which a fourth or upper ball is caused to rotate about a vertical axis under prescribed conditions of load and speed.
• the contacting surfaces on the f our-ball type apparatus are geometrically well-defined, thus providing obvious advantages in the study of wear and friction phenomena.
• the points of contact are lubricated by the fluid under test, which is held in a cup surnounding the four-ball assembly.
• the weld point of the balls was determined by having them immersed in the test lubricant and gradually increasing the load on the balls by increment-s of 10 kgm. until the balls were welded together in a one minute test period.
• compositions comprising the polyphenyl ether fluids and the oxygenated organic tin compounds were also submitted to the Falex anti-weld test [see, e.g., the articles by V. A. Ryan in Lubrication Engineering, September 1946 and by S. Kyropoulos in Refiner Natural Gasoline Mfr., 18, 320-24 (1939)].
• Falex anti-weld test there was employed a Faville-LeVally Falex lubricant testing machine with heating element, 4,500 lb. pressure gage indicating bearing loads, calibrated, circular, toothed loader capable of providing wear estimates, and torque indicating gage.
• the machine is essentially a device in which a pin is rotated between two V-shaped bearing blocks which are immersed in an oil cup containing 55 ml.
• the bearing blocks are inserted in self-aligning recesses in the short lever arms, or jaws, of the loading-applying mechanism. Pressure is applied through the loading mechanism which fits loosely over the bifurcated ends of the long lever arms.
• the ratchet wheel is turned up by hand until the loading mechanism takes hold, which is indicated by registration of applied load on its attached gage. Additional load is applied by engaging the load-applying arm with the ratchet
• the eccentric motion of the load-applying arm increases the application of load, one tooth at a time.
• the entire mechanism is free to swing about its axis, this tendency to turn being resisted by the syphon o erated 9 gage which registers torque in pound-inches. In the present tests, the machine was operated at 290 r.p.rn.
• the antioxidant effect of the present oxygen-containing organic tin compounds on the polyphenyl ether fluids was determined by bubbling air through duplicate samples at 600 F. for a specified time (generally 24 or 48 hours) and then determining the viscosity (at 100 F.) and percent loss in weight of the treated sample. The percent change in viscosity (before and after oxidation) is taken as an index of anti-oxidant activity. Since the presence of metals also has been found to have an effect on the oxidation of polyphenyl ether fluids at high temperatures, in many instances the testing was also conducted in the presence of metals. In order to determine metal eflect, one set of duplicate samples of ether fluid and additive, copper, steel, aluminum and silver wires, whereas another duplicate set contained only 'the ether fluid and additive.”
• Example 1 A mixure of 5.5 g. (0.05 mole) of hydroquinone, 38.5 g. (0.1 mole) of triphenyltin chloride and 6.6 g. (0.1 mole) of 85% potassium hydroxide in benzene as diluent was refluxed in a flask equipped with a Dean-Stark trap under nitrogen for 5 hours. The resulting reaction mixture was filtered and the filtrate poured into petroleum ether to precipitate the substantially pure p-bis(triphenylstannoxy)- benzene, a white solid, M.P. 133-l35 C.
• the compound was tested for use as antioxidant for a mixture of polyphenyl ethers consisting by weight of 65% of m-bis(m-phenoxyphenoxy)benzene of m- (m-phenoxyphenoxy) (p-phenoxyphenoxy) benzene 5 of m-bis(p-phenoxyphenoxy)benzene.
• Test samples containing 1.0 g. of the p-bis(triphenylstannoxy)benzene and 100 g. of said mixture of ethers were prepared. Into one duplicate set of the samples there were immersed weighed pieces of iron, copper, aluminum and silver wire. Controls, i.e., samples containing no additive and with or without the same metals, were set up. The viscosity of all the test samples were determined at 100 F. The samples were heated to 600 F. and air was bubbled into the heated samples for 24 hours at a rate of 1 liter per hour. At the end of this time, the following results were obtained.
• the sample of the ether mixture alone, had a viscosity of 370.58 cs. before the test and a viscosity of 570.7 cs. after the test, i.e., there was a 54.07% change; but the viscosity of the ether mixture plus additive rose only from 373.29 to 409.69, i.e., there was only a 9.75% change.
• There was no change in the weight of ether mixture plus additive before and after the test which fact shows 0.00 evaporation of the p-bis(triphenylstannoxy)benzene.
• the viscosity rose from 370.58 to 515.1 (39.0%) in absence of the additive and from 373.29 to 406.05 (8.78%) in presence of the additive.
• Example 2 A 20 g. sample of triphenyltin chloride was dissolved in 100 ml. of benzene, with stirring. To the stirred solution there was added 20 g. of sodium hydroxide dissolved in ml. of water. The mixture became turbid and stirring was continued for 2 hours. Separation of the layers and evaporation of the benzene solvent layer gave 17.0 g. of the substantially pure bis(triphenyltin) oxide, 21 white 10 soild, MP. l20124 C., analyzing 59.52% carbon and 4.54% hydrogen as against 60.38% and 4.22%, the re spective calculated values for C H Sn O.
• Example 3 A mixture of 34.3 g. (0.1 mole) of the diphenyltin dichloride and 20.0 g. (0.212 mole) of chloroacetic'a'cid was refluxed in toluene for 12 hours. The solvent was then removed under reduced pressure to obtain as residue the substantially pure diphenyltin bis(chloroacetate), a viscous, black oil.
• Example 2 Evaluation of the chloroacetate as an antioxidant for polyphenyl ether fluid was conducted as in Example 1, except that air was introduced for 48 hours in the absence of the metal wires.
• the viscosity of the mixture of ethers, containing no additive rose from 371 cs. to 725 cs. (95.8% increase) as a result of the treatment, whereas in the presence of said chloroacetate it increased from 371 cs. to only 462 cs. (24.2%).
• Example 4 Dibutyltin bis(2-ethylhexoate) (from dibutyltin dichloride and Z-ethylhexanoic acid) was evaluated as an antioxidant for polyphenyl ether fluid using the procedure described in Example 1. After the 24 hour period of air-flow, the viscosity of the ether fluid, alone, was 570.7 cs., whereas that of the ether fluid plus the Z-ethylhexoate was 464.38 cs.
• Example 5 A mixture of 13.3 g. (0.05 mole) of diphenyltin dichloride and 16.3 g. (0.1 mole) of trichloroacetic acid was refluxed in toluene with stirring. The colorless reaction mixture turned almost black when the reflux temperature was reached. The mixture was cooled to room temperature and the solvent was removed under reduced pressure. There was thus obtained as residue the substantially pure diphenyltin bis(trichloroacetate), a green viscous oil.
• the modification of anti-wear and extreme pressureresisting characteristics by the diphenyl bis(trichloroacetate) was determined for the mixture of polyphenyl ethers of Example 1 by the hereinbefore described testing procedures.
• the weld point was greater than 720 kg. as against kg., the weld point value for the mixture of ethers in the absence of an additive.
• the Falex test reading for the polyphenyl ether mixture plus trichloroacetate was greater than 4500, whereas that for the ether mixture only was 500.
• Example 6 Bis(phenylthio)diphenyltin was tested as an antiwear and extreme pressure-resisting additive for the mixture of polyphenyl ethers described in Example 1. Evaluation was conducted as hereinbefore described, using 5 g. of the bis(phenylthio)diphenyltin per 100 g. of the mixture of ethers. There was thus obtained a weld point of 230 kg. and a scar diameter of 1.26 mm. at 40 kg. and 600 F., as compared to a weld point of 150 kg. and a scar diameter of 2.92 at 40 kg. and 600 F. for the mixture of polyphenyl ethers in the absence of an additive.
• Example 7 Sodium carbonate (0.2 mole) was added to a benzene solution of 34.4 g. (0.1 mole) of diphenyltin dichloride 1 1 and 17 g. (0.1 mole) of p-xylene-a,ot-dithiol. The mixture was refluxed for 2 hours and filtered hot. Upon addition of petroleum ether to the filtrate, Stratification occurred. The upper layer of solvent was decanted, and the residue was Washed three times with ether and freed of solvent by evacuation in a vacuum desiccator to give the substantially pure viscous, polymeric product consisting of the repeating unit Evaluation of the above-obtained polymer as an antioxidant for polyphenyl ether fluid was conducted as in Example 1. At the end of the 24 hour test period in the absence of the metal wires there was a significant decrease in viscosity and no change in weight of the samples which contained said polymeric product.
• Example 8 Bis(pentachlorophenylthio)dibutyltin was tested as an anti-wear and extreme pressure-resisting additive for the mixture of polyphenyl ethers of Example 1. Evaluation was conducted at a concentration of 2 g. of the tin compound per 100 g. of said mixture of ethers, employing the hereinbefore described procedures. There was thus obtained a weld point of 210 kg. as against 140 kg., the value obtained for the ether mixture in the absence of an additive, and a scar diameter of 1.31 mm. at 40 kg. and 400 F. and 1.29 mm. at the same pressure and 600 F. as against 2.12 mm. and 3.05 mm., the corresponding similarly obtained values for the mixture of polyphenyl ethers, alone.
• Example 9 A mixture of 0.1 mole of diphenyltin oxide and 0.2 mole of pentachlorophenol was refluxed in toluene as diluent under a Dean-Stark trap until substantially 0.1 mole of Water had collected. The toluene was removed by distillation under partial vacuum and the residue was crystallized from dioxane-water to give the substantially pure bis[(pentachlorophenoxy)diphenyltin] oxide, white crystals, M.P. 157170 C. and having the structure in m This compound was tested as an anti-wear additive for the polyphenyl ether fluid of claim 1, employing the herein described four-ball testing procedure. There was thus obtained a scar diameter of 1.26 mm. at 40 kg. and 600 F. as compared to 2.92 mm., the value obtained for the mixture of polyphenyl ethers, alone, under the same testing conditions.
• the polyphenyl ether component may be any one polyphenyl ether having from 4 to 7 benzene rings.
• the bis(triphenylstannoxy)benzene of Example 1 or the bis(triphenylt in) oxide of Example 2 is a very good antioxidant fior any one of the three ethers of the polyphenyl ether mixture of Example 1, as well as for such other polyphenyl ethers as p-bis-[p-(m-phenoxyphenoxy)phenoxy] benzene, or m (m-phenoxyphenoxy) (o-phenoxyphenoxy)]benzerie, or in bis[m (p-phenoxyphenoxy) phenoxy1benzene, or mixtures thereof in any proportion.
• Lubricant mixtures of ethers are generally so constituted as to give simultaneously an optimum of thermal stability and lubricity at the temperatures to which they will be exposed in operation; but since the polyphenyl ethers, generally, are benefited by the organic tin-oxygen and/ or or tin-sulfur compounds With respect to increasing stability to oxygen and/ or film strength under conditions of high pressure at high temperatures, mixtures having varying proportions of the ethers are advantageously modified.
• the additive belongs to the general class of organotin-oxygen or organotin-sulfur compounds hereinbefore defined and the polyphenyl ether fluid consists of polyphenyl ethers having from 4 to 7 benzene rings.
• organotin-oxygen or organotinsulfur compounds confer a variety of beneficial properties to the polyphenyl ether fluids, they may be used with other additives, e.g., pour point depressants, viscosity index improvers, crystallization suppressants, dyes, etc.
• a functional fluid composition consisting essentially of a polyphenyl ether of the formula wherein n is a whole number from 2 to and from 0.1% to 10.0% by weight of the ether, of an organotin compound having a formula selected from the class consisting of where n is a number of from 2 to 3, m is a number of l to 2 and the total of m+n is 4, R is selected from the class consisting alkyl radicals of from 1 to 12 carbon atoms, benzenoid hydrocarbon radicals which are free of olefinic and acetylenic unsatura-tion and contain from 6 to 12 carbon atoms and such radicals carrying halogen substitution at the benzenoid nucleus, and aryloxyaryl radicals of from 12 to 24 carbon atoms; R is selected from the class consisting of R, paralfinic and haloparaffinic acyl radicals of from 2 to 12 carbon atoms, the radical wherein Z denote the necessary members to complete
• composition defined in claim 1 further limited in that the organotin compound has the formula in which R is a saturated benzenoid hydrocarbon radical of from 6 to 12 carbon atoms.
• composition defined in claim 1 further limited in that the organotin compound has the formula wherein R is phenyl and R is a haloalkyl radical of from 1 to 12 carbon atoms.
• composition defined in claim 1 further defined in that the organotin compound has the formula it (alk) zSn(O U-allr);
• alk denotes an alkyl radical of from 1 to 12 carbon atoms.
• composition defined in claim 1 further defined in that the organotin compound has the formula wherein R is a saturated benzenoid hydrocarbon radical of from 6 to 12 carbon atoms.
• composition defined in claim 1 further limited in that the organotin compound has the formula X--SInX-alkylenearylenealkylenein which X is a chalcogen element having an atomic weight of less than 33, alkylene has 1 to 4 car-hon atoms and arylene has 6 to 12 carbon atoms, and R is a saturated benzenoid hydrocarbon atom of from 6 to 12 carbon atoms, the number of said repeating units in the polymer being from 10 to 1000.
• X is a chalcogen element having an atomic weight of less than 33
• alkylene has 1 to 4 car-hon atoms
• arylene has 6 to 12 carbon atoms
• R is a saturated benzenoid hydrocarbon atom of from 6 to 12 carbon atoms, the number of said repeating units in the polymer being from 10 to 1000.
• composition defined in claim 1 further limited in that the organotin compound has the formula wherein alk is an alkyl radical of from 1 to 12 carbon atoms and R is a saturated, halgen-substituted benzenoid hydrocarbon radical of from 6 to 12 carbon atoms.
• composition defined in claim 1 further limited in that the organotin compound has the formula in which R is a saturated halogen-substituted benzenoid hydrocarbon radical of from 6 to 12 carbon atoms and R is a saturated benzenoid hydrocarbon radical of from 6 to 12 carbon atoms.
• composition defined in claim 1 further limited in that the organotin compound is p-bis(triphenylstannoxy)benzene.
• composition defined in claim 1 further limited in that the organotin compound is bis(triphenyltin)oxide.
• composition defined in claim 1 further limited in that the organotin compound is diphenyltinbis(chloroacetate).
• composition defined in claim 1 further limited in that the organotin compound is dibutyltin bis(2-ethylheXoate).
• composition defined in claim 13 further limited in that the organotin compound is diphenyltin bis(trichloroacetate 14.
• organotin compound is bis(phenylthio)diphenyltin.
• composition defined in claim 15 further limited in that the organotin compound is a polymer having the repeating unit the number of said repeating units in the polymer being from 10 to 1000.
• composition defined in claim 1 further limited in that the organotin compound is bis(pentachlorophenylthio)dibutyltin.
• composition defined in claim 1 further limited in that the organotin compound is bis(benzothiazolylthio)dibutyltin.
• composition defined in claim 1 further limited in that the organotin compound is bis[(pentachlorophenoxy)diphenyltin] oxide.

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  • NL NL292701D patent/NL292701A/xx unknown
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• 1962
  • 1962-05-14 US US194650A patent/US3290247A/en not_active Expired - Lifetime
• 1963
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