JP2014206548A - Optically active functional fluid marker - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optically active functional fluid marker.SOLUTION: The present invention relates to a method of identifying fluid by measuring the amount of optical rotation the fluid causes in a beam of polarized light. The invention further provides use of an optional optically active marker in the fluid in order to effect the amount of rotation the fluid causes. The invention provides convenient and reliable means for identifying the fluid before, during and/or after use of the fluid. Another object of the invention is to provide a method to analyze functional fluid rapidly in the field. Further, another object of the present invention is to provide a method to test an attribute of the functional fluid in the field rapidly by untrained personnel and without precision measurement.

Description

  The present invention relates to determining the identity of a fluid, such as an organic fluid. In particular, the present invention provides a convenient and reliable means for identifying fluids before, during and / or after use of the fluid. The invention also relates to a system for identifying a fluid by passing a polarized beam through a sample of fluid and measuring the amount of optical rotation caused by the sample. The present invention further provides for the use of optically active markers that increase and / or adjust the amount of rotation observed from the sample. This measurement of rotation caused by the material in the fluid being tested, including an optional optically active marker, allows the fluid to be identified.

  Different types of fluids are used in many very different applications. In all of the various types and uses of fluids, it is often required to identify the fluid and / or source of the fluid, and the means for identifying the fluid is convenient and reliable. Is required.

  Functional fluids as defined in this application are those fluids used in various automobiles, off-road vehicles, on-highway vehicles, equipment, machinery, metalworking, and industrial applications. It is important to know the attributes of such functional fluids to prevent improper use or unauthorized counterfeiting of functional fluids. The proper functional fluid can help ensure the good condition of the device and / or apparatus that contains the functional fluid and can affect warranty agreements. Therefore, it is desirable to be able to determine such functional fluid attributes.

  There are methods for analyzing and identifying fluids using various reagents to determine the presence and / or concentration of various components of the fluid. Certain reagents may be used to determine the presence and concentration of components in the functional fluid. These methods typically use reactive reagents on the test strip to analyze pH, colorants, and contaminants. These methods generally also require controlled conditions for the reactive reagents to function properly. Furthermore, these methods are subjective and can be inaccurate.

  Markers have been used to identify fluids. Proton accepting chemicals have been presented as markers or taggants, particularly for petroleum-derived fuels. The marker is subsequently detected by dissolving in the identified liquid and then performing a chemical test on the marked liquid. Markers are sometimes used by government agencies to ensure that appropriate taxes are paid for specific grades of fuel. Oil companies also mark their products to help support the identification of diluted or modified products. These companies often spend a great deal of money to ensure that each branded product meets certain specifications, as well as to provide products with effective additive packages. The consumer relies on the product name and quality label to believe that the purchased product is of the desired quality. Therefore, it is important to be able to identify markers in petroleum products.

  Traditionally, the presence of a marker substance is detected by extracting the fluid with an aqueous or highly aqueous solution of an acid substance whose optional properties can vary depending on the marker substance, and optionally Quantified. The acid reacts with the marker compound to produce an easily visible somewhat intensely colored cation dissolved in the aqueous acid phase. This method is disclosed in Patent Document 1. Furthermore, Patent Document 2 discloses a method for attaching an acidic substance to a test piece. The test piece is immersed in oil, the diazo type marker is reacted with the acidic substance of the test piece, and the color changes.

  In many of these methods, fluid extraction will typically need to be repeated two or three times to recover a sufficient amount of marker for complete quantification. Furthermore, the extracted separated phase can often be classified as hazardous waste, presenting problems with safe and legitimate disposal, especially when the inspection is done “in the field”. Furthermore, the functional fluid being tested can be contaminated by the process, and it is undesirable to return this fluid to its original source, which presents additional waste disposal issues.

  Many owners / users of these fluids, operator of the equipment, and / or retailers of these fluids are now able to use certain attributes of the fluid when such questions arise, such as in warranty resolutions. Rely on off-site laboratories to determine. Tools that can identify fluids in the field are thought to be able to expedite cocoon elucidation and similar tasks.

US Pat. No. 5,145,573 International Publication No. 03/078551

  An object of the present invention is to provide an easy and convenient delivery system for accurately analyzing fluid attributes. Another object of the present invention is to provide a method for rapidly analyzing functional fluids in the field. Another object of the present invention is to provide a method for quickly testing functional fluid attributes in the field by an untrained person and without accurate measurements. Yet another object of the present invention is to provide a diagnostic kit for rapidly identifying functional fluids in the field.

  The present invention is a method for determining an attribute of a functional fluid comprising: (1) adding an optional optically active marker component to the fluid; (2) prior to use of the fluid sample in the application; Obtaining a sample of the fluid during or after; (3) passing a polarized beam through the sample; (4) measuring the rotation of the plane of light after the light has passed through the sample; 5) providing a method comprising determining a fluid attribute according to the amount of rotation observed;

  The present invention further provides for the use of chiral molecules as optically active markers, which chiral molecules are at least partially soluble in the fluid. The optically active marker component used in the method of the invention is non-racemic with respect to at least one set of enantiomers.

The present invention further includes a source of polarized light, means for directing the polarized beam from the source into the fluid sample, and means for detecting the amount of rotation of the polarized beam after it has passed through the sample. And a diagnostic kit for analyzing the fluid comprising means for communicating the results from the analyzer to the user. The kit may include written instructions, pictures, diagrams, and / or photographs to assist the user in fluid identification. Fluids used with such diagnostic kits may include optically active markers.
Accordingly, the present invention provides the following items:
(Claim 1)
(1) adding an optional optically active marker component to the functional fluid;
(2) obtaining in the application a sample of the fluid before, during or after use of the sample of fluid;
(3) passing a polarized beam through the fluid sample;
(4) measuring the rotation of the plane of the light after the light has passed through the fluid sample by comparing it to the original orientation of the light;
(5) A method for determining an attribute of a functional fluid including the step of determining the attribute of the fluid according to the amount of rotation observed.
(Section 2)
Item 2. The method of Item 1, wherein the optically active marker component comprises a chiral molecule that is at least partially soluble in a functional fluid.
(Section 3)
The optically active marker component is a compound of the following formula:

Wherein X is C, N, P, or S; R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrocarbyl group, —OR ⁵ group (R ⁵ is hydrogen or A hydrocarbyl group), an aromatic group, a lone pair of electrons (when X is N), a double-bonded oxygen atom (when X is P or S), provided that none of the R groups are the same. On condition that there is no)
Item 3. The method according to Item 1 or 2, wherein the optically active marker component is non-racemic with respect to at least one set of enantiomers.
(Claim 4)
The above fluids are automatic transmission fluid, engine oil, traction drive transmission fluid, manual transmission fluid, power steering fluid, antifreezing fluid, lubricating oil, grease, crankcase lubricant, mineral oil, group 1, 2, 3 or 4 Oil with oil, differential lubricant, turbine lubricant, gear lubricant, gearbox lubricant, axle lubricant, brake fluid, farm tractor fluid, transformer fluid, compressor fluid, cooling system fluid, metalworking fluid, hydraulic Item 4 is selected from the group consisting of fluid, industrial fluid, passenger car fuel, diesel engine fuel, bio-based fuel, continuously variable transmission fluid, continuously variable transmission fluid, and mixtures thereof. the method of.
(Section 5)
Item 5. The method according to any one of Items 1 to 4, wherein the marker component is added to the fluid before or during use of the fluid in application.
(Claim 6)
Item 6. The method according to any one of Items 1 to 5, wherein the concentration of the marker component in the functional fluid is 10 ppm to 1000 ppm.
(Claim 7)
The optically active marker component is cholesteryl acetate, one or more tartaric acid-derived diesters and / or imides, L-menthyl lactate, S-(−)-perylaldehyde, (1R)-(−)-menthyl acetate, R Item 7. The method according to any one of Items 1 to 6, comprising-(+)-limonene, cholesterol, sucrose, camphor, penicillin V, taxol, bromobutane, kabiclarin, or a combination thereof.
(Section 8)
A source of polarized light, means for directing a polarized beam from the source into a fluid sample, and means for detecting the amount of rotation of the plane of the polarized beam after the beam has passed through the sample; A diagnostic kit for analyzing a fluid comprising means for communicating results from the analyzer to a user, in order to assist the user in identifying the fluid, written instructions, pictures, A diagnostic kit further comprising a figure, a photograph, or a combination thereof.
(Claim 9)
Item 9. The diagnostic kit according to Item 8, wherein the fluid contains at least one optical marker.

  The present invention uses the measured optical rotation as a means to identify and / or confirm the source of fluid, including devices such as methods and kits, to analyze and monitor various fluid attributes. I will provide a. The present invention further provides an optical marker that affects the ability of the fluid to rotate the polarization. These markers may be used in the methods, devices, and kits described herein to identify and / or confirm fluid sources and / or monitor fluid attributes. May be used.

Fluids to be identified Fluids suitable for use in the present invention are not unduly limited, as the methods and optically active markers described herein may be used to identify the fluids. In general, the methods and optically active markers described herein may be used with any liquid or fluid that is sought to confirm and / or determine the source and / or attributes of the fluid. More specifically, the method of the present invention is directed to functional fluids such as lubricants and fuels and industrial fluids.

  Suitable fluids include functional fluids derived from countless sources, including, for example, internal combustion engines, stationary engines, turbines, transmissions, differentials, pumps, metalworking operations, cooling systems, and industrial systems. It is. Functional fluids include automatic transmission fluid, continuously variable transmission fluid, continuously variable transmission fluid, traction drive transmission fluid, manual transmission fluid, power steering fluid, antifreezing fluid, lubricant, grease, crankcase lubricant, cylinder lubricant , Mineral oil, Group I, II, III, or IV base oil, differential lubricant, turbine lubricant, gear lubricant, gearbox lubricant, axle lubricant, farm tractor fluid, transformer fluid, compressor fluid, cooling system Fluids, metalworking fluids, hydraulic fluids, brake fluids, industrial fluids, fuels, continuously variable transmission fluids, and the like. In one embodiment, the functional fluid is an automatic transmission fluid. In one embodiment, the functional fluid is a power steering fluid. In one embodiment, the functional fluid is an internal combustion fuel such as gasoline and / or diesel. In one embodiment, the functional fluid is a compressor fluid, such as an air compressor lubricant and / or a turbine lubricant. In one embodiment, the functional fluid is an internal combustion engine oil. In one embodiment, the functional fluid is tested when a certain amount of time in use has passed until a period including the useful life of the fluid.

  In some embodiments, the fluid is organic and does not contain any aqueous material other than a small amount commonly caused by contamination. In such embodiments, the fluid may contain less than 10% water, or less than 5%, less than 1%, or even less than 0.5% water. In other embodiments, the fluid includes both organic and aqueous fluids, and mixtures thereof.

  Non-fluid materials may be used in the present invention, in which case the non-fluid material is dissolved in a solvent, melted, or otherwise transferred into a fluid medium for testing.

  Many fluids contain materials that rotate the plane of polarized light. This rotation measurement may be used to verify fluid attributes, as described below. Such materials inherently contain optically active materials that may be used as markers in the methods of the present invention. The present invention includes a method for measuring the optical rotation of such materials, using the observed rotation as a means of identifying a fluid. In some embodiments, the fluid may not cause any significant rotation and / or may not rotate the light more or less than competing products, counterfeit products and / or alternative products. In such cases, the present invention further provides for the use of optically active markers that may be added to the fluid to provide various levels of optical rotation. Thus, fluids containing optional markers can then be tested by the methods of the present invention, and the observed optical rotation adjusted by the use of the optical markers described herein is a property of the fluid. May be used to identify and / or verify.

Solvents Used with Markers In embodiments where optical markers are added to the fluid, the markers may be added to the fluid, with which the marker is used as an untreated component. In other embodiments, the marker may be present in a mixture comprising one or more optical markers and further comprising one or more solvents as described herein, and the marker concentrate or marker A solution may be formed and then added to the fluid. The mixture may further include additional materials such as, but not limited to, performance additives designed to affect and / or improve the performance of the resulting functional fluid. .

  As described above, a suitable solvent may be used with the marker to form a marker solution. The solvent used depends on the type of functional fluid being tested, the delivery system used, and the marker used. Solvent combinations are also useful when the marker does not dissolve in the functional fluid, depending on the application and the type of analysis desired. The solvent or combination of solvents may be selected by considering the desired properties including good solvency and miscibility with functional fluids and markers, low vapor pressure at ambient temperature, high flash point, etc. Good.

  Suitable solvents include aliphatic, unsaturated, and aromatic hydrocarbons, polyols such as alcohols, glycols, glycol ethers, glycerol, lower alcohols such as methanol, ethanol, and propanol, ethers, esters, amides, amines, and Contains water. Combinations of solvents may be used.

  In some embodiments, a marker component that refers to a mixture of a marker and any optional solvents and / or additional additives that may be present is any material that is believed to inhibit the optically active properties of the marker compound. Is not included. In other embodiments, the marker component does not include any material that will react with the optically active marker present. In other embodiments, the marker component does not include any non-chiral and / or non-optically active components.

  The term marker and / or marker component, as used in this application, unless otherwise indicated, the one or more marker compounds per se without added solvent or one or more marker compounds And a marker solution comprising a mixture of one or more solvents or additional additives. The solvent may be present in the marker solution in the range of about 1% to about 99.99% by weight, and in one embodiment about 5% to about 98% by weight of the marker solution, another embodiment. May be present in the range of about 1% to about 95.5% by weight.

Optically active marker The marker material is selected to be compatible with or not compatible with the fluid used together and / or the system where the fluid is used. In one embodiment, the marker is selected to survive in the application and / or use conditions where the functional fluid is exposed during its use.

  In one embodiment, the marker material is used to identify new and / or unused fluids. In other embodiments, it is useful to demonstrate the attributes of the fluid used, for example for warranty rights. In this case, the marker needs to persist and be detectable after facing typical fluid handling and / or usage conditions. In the case of a functional fluid, this may include surviving operation of the engine or other device in which the functional fluid is used.

  A marker suitable for use in the present invention may be described as an optically active marker. Suitable optical markers are: one or more compounds comprising a chiral molecule; one or more compounds wherein the molecule contains at least one chiral center, axis or plane; the molecule is at least one four-sided One or more compounds containing a body-bound atom and differing in all four substituents on the tetrahedral bond atom; or a mixture of one or more of the compounds described above. In all of the above embodiments, the mixture of markers used must have an overall enantiomeric excess such that the optically active system is present to rotate the plane of polarization.

  In one embodiment, the marker of the present invention comprises one or more compounds represented by Formula I shown below:

Wherein X is C, N, P, or S; R ¹ , R ² , R ³ , and R ⁴ are each independently a hydrocarbyl group, —OR ⁵ group (R ⁵ is hydrogen or A hydrocarbyl group), an aromatic group, a lone pair, a double-bonded oxygen or nitrogen atom (when X is P or S), provided that each R group is unique and each R group Is provided that it may contain a functional group, that is, R ¹ , R ² , R ³ , and R ⁴ are each a unique substituent, and R ¹ ≠ R ² ≠ R ³ ≠ R ⁴ ).

  In some embodiments, the optically active marker is: soluble in the fluid being marked; exhibits a measurable optical rotation of the appropriate wavelength of light; an application in which the fluid is used or where the fluid is used Does not harm the examples; colorless in the visible spectrum and / or does not affect the color of the marked fluid; odorless and / or tasteless and / or the odor of the marked fluid and / or Or does not affect the taste; or some combination of these.

  The marker may be soluble in the fluid from 0.00001% to 100% by weight. Suitable wavelengths of light that cause suitable markers to cause rotation include ultraviolet light, visible light, infrared light, or combinations thereof. Sufficient optical rotation may be an amount greater than the range of errors in the measurement device used to evaluate the rotation, and in some embodiments, the rotation is at least 0.1 degrees, at least 0. 5 degrees, at least 1 degree, or rotation is at least 5 degrees. Although optical rotations greater than 360 degrees are possible, in the present invention, molecules that rotate light greater than 360 degrees are characterized as having an optical rotation minus 360 from their actual rotation.

  A compound is considered optically active if it can rotate the plane of polarized light passing through it. The amount of optical rotation is determined by the molecular structure and concentration of optically active molecules in the fluid, the wavelength of light passing through the fluid, the path length involved, and the temperature. Each optically active material provides its own specific rotation, defined by Biot's law:

(Where [α] = specific optical rotation, T = temperature, λ = wavelength, α = optical rotation, c = concentration in g / 100 ml, l = optical path length in dm). The rotation caused by the optically active compound is obtained from the interaction between the chiral material and the polarized light. Certain enantiomers of chiral molecules absorb polarized light to varying degrees. Enantiomers can be named by the direction in which the plane of polarization is rotated. When the light is rotated clockwise (as seen by an observer in the direction of light travel), the enantiomer is labeled as (+) or dextrorotatory and labeled as “d−”. Is done. The mirror image is labeled “-”, or “l-” derived from levorotatory.

  An optically active compound may be labeled by identifying each isomer by the spatial arrangement of its atoms using R / S designation. The R / S system does not have a fixed relationship to the (+) / (−) or d− / l− system described above. The R / S system labels each chiral center present in the compound with R or S, depending on the system on which the priority is given to the substituent at the chiral center, based on the atomic number. When the chiral center is oriented so that the substituent with the lowest priority points away from the observer, the observer sees two possibilities: the priority of the other three substituents When R is decreasing in the clockwise direction, the chiral center is labeled R with respect to the right (Rectus); when the preference of the substituent is decreasing in the counterclockwise direction, the chiral center is with S as the left (Sinister). Labeled. This system labels each chiral center (and / or each chiral plane, chiral axis, and / or chiral group) of the molecule and thus has a higher generality than the other systems described above.

  Optically active compounds include chiral molecules. The term chiral is used to describe an object that cannot be superimposed on its own mirror image. A chiral molecule can have a “point chirality” in which the chirality of the molecule is centered on a single atom, usually a carbon atom, having four different substituents. A molecule is chiral if all four substituents on a tetrahedral bond atom are different. Isotope differences are sufficient for chirality.

  The above definitions for chiral molecules are not limited to tetrahedral carbon atoms, but also include any other type of central atom with the appropriate set of substituents or ligands. Examples include appropriately substituted octahedrons and other coordination structures, including metal complexes and inorganic structures. Furthermore, the molecule may have multiple chiral centers. Molecules can also be chiral without point chirality. Common examples include 1,1'-bi-2-naphthol (BINOL) and 1,3-dichloro-allene with axial chirality, and (E) -cyclooctene with planar chirality.

  The asymmetric center of a chiral molecule need not be located on a specific atom. For example, an adamantane derivative having a suitable substituent may be chiral. In these structures, the entire group retains four substituents in spatial configuration as opposed to a single atom, and the compound cannot overlap its mirror image.

  There are many examples where the chirality of a molecule arises from a constrained rotation of the group or spatial configuration of the chiral moiety, some of which include 1,2,3,4-tetramethyl-cyclooctatetra Ene, 2,5-dimethyl-bicyclo-2,2,2-octa-2,5,7-triene, and perchloro-triphenylamine. Furthermore, catenanes and molecular nodes made from achiral molecules may be chiral.

  A chiral substance is considered enantiopure or homochiral if only one of the two possible enantiomers is present, and an equal mixture of the two enantiomers is referred to as a racemic mixture. A chiral material is enantiomerically enriched or heterochiral if there is an excess of one enantiomer but not the other. Enantiomeric excess is a measure of how much one enantiomer is present compared to the other. Non-racemic chiral mixtures may be referred to as scalemics.

  In some embodiments, the present invention uses one or more optically active markers where the marker component and / or mixture is not a racemic mixture. That is, the marker component is scalemic and has a certain enantiomeric excess or optical purity of less than 100%. In some embodiments, the present invention requires that the mixture of optically active markers contains at least a 5 wt% excess of one enantiomer for each optically active marker present. In still other embodiments, the excess should be 20%, 50%, or even 75% by weight.

  The marker of the present invention includes the following substances: abscisic acid, sulfoxime, sulfonamide, sultam, 1-acetoxycarbicol acetate, acenaphthenol, alfuzosin, alprenolol, althiazide, 1-aminoindan, amlodipine, anisoin, 9-anthrylethanol, 9-anthryltrifluoromethylcarbinol, arginine, atenolol, atropine, azelastine, bambuterol, bendroflumethiazide, benzoin, 1- (4-benzyloxy) phenyl, ethanol, β-naphthylmethylcarbinol , Betaxolol, bifonazole, 1,1′-binaphthol monomethyl ether, 1- (p-bromophenyl) ethanol, brompheniramine, buckminsterfullerene-enone [2 + 2] Adducts, bufuralol, bupivacaine, bupranolol, caranolide, carazolol, carprofen, carvedilol, chlorflurecol methylchlormezanone, 4-chloromandelic acid, 2- (2-chloro-4-methylphenoxy) propionic acid, 2- (3 -Chlorophenoxy) propionic acid, 1- (m-chlorophenyl) ethanol, 1- (o-chlorophenyl) ethanol, 1- (p-chlorophenyl) ethanol, chlorthalidone, cycloprofen, citalopram, clenbuterol, cromakalim, crotoxiphos, cyclande 1-cyclohexyl-1-phenylacetic acid, 1-cyclopentyl-1-phenylacetic acid, cyclopentylbenzoyl-diamide, cyclophosphamide, cyclothiazide, cyclothiazide-1, co Mubretastatin D-1, cumulolol, cypermethrin, debrinol, napropamide, dexmedetomidine, 2,2'-diaminobinaphthalene, 2,3-dibenzoyl-tartaric acid, diclohopmethyl, dihydrotetrabenazine, diltiazem, dimethyl (1- Acetoxy-3-phenyl-E-propenyl) phosphonate, dimethyl (1-hydroxy-3-phenyl-E-propenyl) phosphonate, 3,5-dimethylanilide-R, S-ibuprofen, dinocup, diperodon, diperodon-1, diperodon -2, diphenylnitroxide, disopyramide-1, disopyramide-2, ditoluoyltartaric acid, dropropidine, doxazosin, EEDQ, etotoin, ethyl-2- (p-hydroxyphenoxy) propionate, ephedrine Etodolac, fenoprofen, fenoterol, phenoxaprop-ethyl, fenvalerate, flavanone, flobfen, flobfen-1, 4-fluorophenylalanine, fluazifopa-butyl, fluridyl, 1- (p-fluorophenyl) ethanol, fluoxetine (prozac) , Flurbiprofen, Formoterol, Glutamine, Glutamic acid, Haloxyhopa-ethoxyethyl, Hanesian lignan, Hesperitin, Hesperitin-2, Hexobarbital, Histidine, Homatropin, Homocysteine thiolactone, Huperzine, Hydroatropic acid, Hydrobenzoin, Hydroxychloroquine 1- (4-hydroxyphenyl) ethanol, p-hydroxy-phenylglycine, 2- (4-hydroxy-phenyl) Noxy) propionic acid, ibuprofen, ibuprofenol, idazoxan, ifenprodil, ifenprodil-2, ifosfamide, indapamide, indapamide-1, indoprofen, ipsdienol, isoxsuprine, isradipine, isradipine-1, ketamine, ketoconazole, ketoprofen, ketoprofen -1-naphthylamide, ketorolac, KP411, kynurenine, lansoprazole, laudanosin, leptophos, phosver, leucine, leucine-1, lorazepam, lorglimide, loxoprofen, luciferin, mandelic acid, McN 5562, mecoprop, mephenytoin, metalaxyl, methadone -1, methionine, a-methoxyphenylacetic acid, 2-methoxyphenylphenylcarbino 1- (4-methoxyphenyl) -2-butanol, 1- (o-methoxyphenyl) ethanol, 1- (4-methoxyphenyl) -2-propanol, methyl mandelate, 1- (o-methylphenyl) ethanol 1- (m-methylphenyl) ethanol, 1- (p-methylphenyl) ethanol, or methyl 3-phenyl-3-azido-2-hydroxypropanoate may be contained.

  Additional examples of chiral compounds include: 3-methyl-5-phenylhydantoin, metolachlor, metolazone, metoprolol, mianserin, modafinil, mosapride, nadifloxacin, nadolol, 1,1'-bi-2-naphthol, a-naphthol methyl Carbinol, 1-naphthyl-2-butanol, 2-naphthyl-2-butanol, 1-naphthylureaphenethylamine, napropamide, naproxen diisopropylamide, naproxen (normal phase), naproxen (reverse phase), naproxen (on ULMO CSP), Naproxen methylamide, naringenin, nicardipine, N-CBZ-valine, nicotine, nimodipine, nilvanol, norleucine, norvaline, octopamine, ofloxacin, omeprazole, omeprazole Prisec), omeprazole-1, oxazepam, oxprenolol, oxybutynin, p-chloro-warfarin, pantoprazole, pazufloxacin, permethrin, pheniramine, phenylcyclohexyl carbinol, 2-phenylcyclopropanecarboxylate, phenylethylcarbi Nord, phenylisopropyl carbinol, phenylmethyl carbinol, 1-[(4-phenyl) phenyl] ethanol, phenylphenyl ethyl carbinol, 1-phenyl-2-propanol, phenylpropyl carbinol, phenyl tribromomethyl carbinol, Phenylalanine, phenylbutyric acid, phenylethylene glycol, phenylglycine, 1-phenylpentanol, phenyl koha Succinic acid, pindolol, pindolol-1, pyrprofen, PPO inhibitor, practolol, praziquantel, prilocaine, proglumide, proline, pronetalol, propaphenone, propiconazole, tilt, propranolol, quizalofop-ethyl, ranolazine, rebamipide, resmethrin , SC 41930, serine, cetoxydim, sotalol, stilbene oxide, styrene oxide, sulconazole, sulfinpyrazone, sulindac, sulpiride, suprofen, taxifolin, temazepam, temazepam-1, terbutaline, terfenadine, terfenadine-2, tert-butyl-2- (Benzamido) cyclopentylcarbamato, separathion, tertbutylphenylcarbinol, tetrabenazine, tetra Drobenzopyrene-7-ol, tetrahydropalmatine, tetrahydropalmatine-2, tetrahydropyrimidine, tetrahydrozoline, 1,2,3,4-tetrahydro-1-naphthol, 1,2,3,4-tetrahydro-1- Naphthylamine, tetramethrin, tetramisol, thalidomide, 2-thiopheneethanol, 3-thiopheneethanol, thiaprofenic acid, timolol maleate, tofisopam, tolperisone, trans-2-phenyl-1-cyclohexanol, trans-11,12-diamino-9, 10-dihydro-9,10-ethanoanthracene, trichloromethiazide, 4- (trifluoromethyl) mandelic acid, 1,1,2-triphenyl-1,2-ethanediol, 1,3,5-triphenylpenta − 4-in-1-one, 1- (m-trifluoromethylphenyl) ethanol, a-trityl-2-naphthalenepropionic acid, Troger's base, troglitazone, Trolox, Trolox-1, Trolox-methyl ether, Tropicamide, tryptophan, tulobuterol HCl, tyrosine, U-100057, U-94863, trans-U-50488H, valine, vanillmandelic acid, vapol, verapamil, verapamil, viloxazine, warfarin (normal phase), warfarin (reverse phase), warfarin ( On ULMO CSP), zopiclone is included.

  Still other examples of chiral compounds include: D-alaninol, L-alaninol, L-(+)-isoleucinol, L-(+)-isoleucinol, L-(+)-leucinol, D-methioninol, L-methioninol. , D-(+)-phenylalaninol, L-(−)-phenylalaninol, D-(−)-α-phenylglycinol, L-(+)-α-phenylglycinol, D-(−) -Prolinol, L-(+)-Prolinol, D-tryptophanol, L-tryptophanol, D-valinol, L-valinol, R-(-)-2-amino-2-phenylethanol, BOC- D-alaninol, BOC-L-alaninol, CBZ-D-alaninol, CBZ-L-alaninol, FMOC-D-alaninol, FMOC-L -Alaninol, BOC-D-(+)-Isoleucinol, BOC-L-(+)-Isoleucinol, CBZ-D-(+)-Isoleucinol, CBZ-L-(+)-Isoleucinol, BOC-D-(+) -Leucinol, BOC-L-(+)-Leucinol, CBZ-D-(+)-Leucinol, CBZ-L-(+)-Leucinol, BOC-D-Phenylalaninol, BOC-L-Phenylalaninol, CBZ -D-phenylalaninol, CBZ-L-phenylalaninol, FMOC-D-phenylalaninol, FMOC-L-phenylalaninol, BOC-D-α-phenylglycinol, BOC-L-α-phenylglycinol FMOC-D-α-phenylglycinol, FMOC-L-α-phenylglycinol, OC-D-prolinol, BOC-L-prolinol, CBZ-D-prolinol, FMOC-D-prolinol, FMOC-L-prolinol, BOC-D-valinol, BOC-L-valinol, FMOC-L -Valinol is included.

  Still other examples of chiral compounds include: S-2-methylpiperazine, R-2-methylpiperazine, S-1-Boc-2-methylpiperazine, R-1-Boc-2-methylpiperazine, S-piperazine -2-carboxylic acid, R-piperazine-2-carboxylic acid, S-4-Boc-piperazine-3-carboxylic acid, R-4-Boc-piperazine-3-carboxylic acid, S-4-Boc-2-methyl Piperazine, R-4-Boc-2-methylpiperazine, S-4-Boc-piperazine-2-carboxyl-t-butyramide, R-4-Boc-piperazine-2-carboxyl-t-butyramide, L-malic acid, D-malic acid, diethyl L-(+)-tartrate, diethyl D-(-)-tartrate, S-2-amino-1-propanol, R-2-amino 1-propanol, S-1-amino-2-propanol, R-1-amino-2-propanol, S-1,2-decanediol, R-1,2-decanediol, S-2-amino-1- Butanol, R-2-amino-1-butanol, S-octanol, R-octanol, S-2-phenylpropylamine, R-2-phenylpropylamine, S-2-heptanol, R-2-heptanol, S-3- Hydroxy-γ-butyrolactone, R-3-hydroxy-γ-butyrolactone, S-2-methyl-1-butanol, R-2-methyl-1-butanol, S-glyceric acid (hemicalcium salt), R-glyceric acid (Hemicalcium salt), S-1-benzylglycerol, R-1-benzylglycerol, S-3-amino-1,2-propanol R-3-amino-1,2-propanol, S-3-methyl-2-butanol, R-3-methyl-2-butanol, S-glycidol, R-glycidol, S-2-methyl-1,4- Butanediol, R-2-methyl-1,4-butanediol, S-3-hydroxyisobutyric acid methyl ester, R-3-hydroxyisobutyric acid methyl ester, S-2-methoxy-2-phenylethanol, R-2 -Methoxy-2-phenylethanol is included.

  Tartrate, tartarimide, similar materials including esters, amides, and imides derived from carboxylic acids such as tartaric acid and citric acid, and these acids themselves may be chiral, Therefore, it is also a marker suitable for use in the present invention. The marker of the present invention may comprise an additive represented by the following Formula I:

Wherein Y and Y ′ are independently —O—,>NH,> NR ³ , or together with Y and Y ′ groups and between two> C═O groups R ¹ — N <There imide group formed by forming a group; X is _{independently, -Z-O-Z '-} ,> CH 2,> CHR 4,> CR 4 R 5,> C (OH ) (CO ₂ R ² ),> C (CO ₂ R ² ) ₂ ,> CHOR ⁶ , or> CHCO ₂ R ² ; Z and Z ′ are independently> CH ₂ ,> CHR ⁴ ,> CR ⁴ R ⁵ ,> C (OH) (CO ₂ R ² ), or> CHOR ⁶ ; n is 0 to 10, or 1 to 8, or 1 to 6, or 2 to 6, or 2 to 4 with the proviso that in the case of n = 1 X is> in CH ₂ without conditions that it is not a n = case 2 both X 'simultaneously> CH ₂ And then; m is 0 or 1; ^{R 1} is independently hydrogen or from typically 30 from 1 150,4 to or 6 to 20 or 10 to 20 or 11 to 18, or 8, A hydrocarbyl group containing 10 carbon atoms, provided that when R ¹ is hydrogen, m is 0 and n is 1 or greater; R ² is typically A hydrocarbyl group containing 1 to 150, 4 to 30, or 6 to 20, or 10 to 20, or 11 to 18, or 8 to 10 carbon atoms; R ³ , R ⁴ , and R ⁵ are independently A hydrocarbyl group, a hydroxyl-containing group, or a carboxyl-containing group; R ⁶ is hydrogen or a hydrocarbyl containing typically 1 to 150, or 4 to 30 carbon atoms. Building group). In one set of embodiments, the hydrocarbyl groups used for R ¹ and R ² contain at least some of the branched hydrocarbyl groups.

  In one set of embodiments, this type of marker is a condensation product of (i), a material represented by Formula II and (ii), a branched alcohol or branched chain having from 1 to about 150 atoms. A mixture comprising amines, or a combination thereof:

Wherein each X is independently —Z—O—Z—,> CH ₂ ,> CR ¹ R ² ,> C (OH) (CO ₂ R ² ), or> CHOR ² ; Z is independently> CH ₂ ,> CR ¹ R ² ,> C (OH) (CO ₂ R ² ), or> CHOR ² ; m is 0 or 1; n is 1 to 10 Provided that when n = 1, X is not> CH ₂ and when n = 2, both X ′ are not> CH ₂ ; each R ¹ and R ² is independently hydrogen or A hydrocarbyl group).

In one embodiment, in Formula II, X is> CHOR ² and n is 2. In another embodiment, in Formula II, (X) n is ^{_{-CH 2 -C (OH) (CO}} 2 R 2) -CH 2 - is. In another embodiment, m in formula II is 1. In still other embodiments, component (i) is tartaric acid, citric acid, a derivative of any acid, or a combination thereof.

  In one set of embodiments, component (ii) comprises a mixture of one or more branched alcohols or amines. In one embodiment, the mixture contains one or more branched alcohols containing 6 to 16 carbon atoms. In another embodiment, the mixture contains a branched amine containing 6 to 16 carbon atoms.

  In another set of embodiments, alone or in combination with any of the above-described embodiments, component (ii) is because at least 25% by weight of the alcohols and / or amines comprising the mixture are branched structures. The entire mixture is composed of a mixture of one or more branched alcohols or amines that are at least 25% by weight branched.

  In some of the above embodiments, the marker may be represented by the following formula or may be in a similar form:

(Where the chiral center of the molecule is identified by an asterisk ( ^* )). There may be more than one chiral center in these molecules, and both carbon atoms positioned between the —COOH groups in Formula III and Formula IV above may be considered chiral centers. Further, each of the —OH groups in Formulas III and IV may independently be an —OR group, where R is a hydrocarbyl group.

  Markers that fit into these categories include diesters derived from tartaric acid. Diesters may be obtained from tartaric acid and alcohols and / or mixtures of alcohols (such as Alfol ™ 810). Specific examples include D-tartaric acid / Alfol ™ 810 diester, L-tartaric acid / Alfol ™ 810 diester, as long as the mixture is non-racemic, ie contains at least one enantiomer in excess. D-tartaric acid / Alfol ™ 1214 tridecyl alcohol diester, L-tartaric acid / Alfol ™ 1214 tridecyl alcohol diester, and mixtures thereof.

  In some embodiments, the markers used in the methods of the invention are tartaric acid and its derivatives, glucose and its derivatives, 2-bromobutane, D-alaninol, D-ananinol, L-alaninol, L-(+)- Isoleucinol, D-leucinol, L-(+)-leucinol, D-methioninol, L-methioninol, D-(+)-phenylalaninol, L-(−)-phenylalaninol, D-(−)-α- Phenylglycinol, L-(+)-α-phenylglycinol, D-(−)-prolinol, L-(+)-prolinol, D-tryptophanol, L-tryptophanol, D-valinol, L-valinol, R-(−)-2-amino-2-phenylethanol, 2-pentanol, 2-fluorobutane, 3-methyl Ruhexane, 2-bromomethyl-2-chloromethyl-1-fluoropropane, N-ethyl-N-methyl-N-propylbutane-1-aminium, m-dichlorocyclohexane and o-dichlorocyclohexane, amino (hydroxy) acetic acid, 1 -Selected from the group consisting of aminoethanol, 2- [pyridin-3-yl (pyridin-4-yl) methyl] pyridine, 2-amino-2-hydroxy-3-oxoacetic acid, and combinations thereof.

  In other embodiments, the markers used in the methods of the present invention are cholesteryl acetate, D-tartaric acid / Alfo 810 diester, L-tartaric acid / Alfo 810 diester, L-menthyl lactate, S-(-)-perylaldehyde, 1R-(−)-menthyl acetate, R-(+)-limonene, L-tartaric acid / Alfo 1214 tridecyl alcohol diester, and combinations thereof, provided that at least one mixture is used As long as it is non-racemic.

  In yet other embodiments: if the fluid involved is a motor oil for a passenger car, the markers are cholesteryl acetate, L-menthyl lactate, S-(-)-perylaldehyde, 1R-(-)-menthyl acetate, R- (+)-Limonene, and combinations thereof; if the fluid is heavy vehicle diesel engine oil, the markers are S-(-)-perylaldehyde, 1R-(-)-menthyl acetate, R -(+)-Limonene, and combinations thereof; when the fluid is an automatic transmission fluid, the markers are cholesteryl acetate, S-(-)-perylaldehyde, 1R-(-)-menthyl acetate, R-(+)-limonene, and combinations thereof; The marker may be L-menthyl lactate, 1R-(-)-menthyl acetate, R-(+)-limonene, and combinations thereof; when the fluid is a hydraulic fluid, the marker is , L-menthyl lactate, 1R-(-)-menthyl acetate, R-(+)-limonene, and combinations thereof; when the fluid is diesel fuel, the markers are cholesteryl acetate, L-menthyl It may be lactate, S-(-)-perylaldehyde, 1R-(-)-menthyl acetate, R-(+)-limonene, and combinations thereof; when the fluid is gasoline, the marker is L- It may be menthyl lactate, 1R-(-)-menthyl acetate, R-(+)-limonene, and combinations thereof.

  In some embodiments, the markers of the present invention have a measurable effect on the optical rotation caused by the fluid in which the marker is used. In some embodiments, this effect is greater than the error range of the test method used. In other embodiments, the marker changes the optical rotation caused by the fluid by at least 5%, at least 50%, or at least 100%.

  If present, the amount of marker present in the fluid is such that as long as there are enough markers to allow accurate identification and there are not so many markers that interfere with fluid performance and / or desired characteristics. It is not overly limited. The marker may be present in the fluid at a concentration of 10 to 10,000 ppm or 10 to 1,000 ppm. In another embodiment, the marker is present in the fluid at 20 to 500 ppm; 25 to 350 ppm, 30 to 130 ppm; or 30 to 100 ppm. In other embodiments, the marker is present in the fluid at a concentration of 0.05 to 10 wt%, or 0.1 to 10 wt%, or 0.5 to 10 wt%. In still other embodiments, the marker is present at greater than 0.05 wt%, or greater than 0.1 wt%.

  The marker compound itself may be soluble in water, substantially soluble in water, substantially insoluble in water, or insoluble in water. In other embodiments, the marker compound is soluble in organic liquids such as oil, is substantially soluble in organic liquids, is substantially insoluble in organic liquids, or is insoluble in organic liquids. The marker compound should be substantially soluble and / or soluble in the fluid in which the compound is used, or substantially in at least one of the components present in the fluid in which the compound is used. Should be soluble and / or soluble.

  The optical markers of the present invention may be used in combination with other markers, including non-optically active markers such as markers that react with reagents so that fluids can be accurately identified. The use of multiple types of markers allows an additional level of protection and accuracy when validating the attributes and / or sources of the fluid under test.

  In another embodiment, a marker compound is added to the functional fluid, and the marker is in the form of a concentrate containing a mixture of the marker compound and the polymer compound. The polymer compound may be one or more conventional additives for functional fluids. In one embodiment, polymeric compounds that may be in the concentrate include dispersants, detergents, antiwear agents, friction modifiers, metal deactivators, corrosion inhibitors, seal swell agents, viscosity modifiers. Agents, pour point depressants, thickeners, and antioxidants are included alone or in combination with each other.

Optional ingredients Optional ingredients may be added to the marker solution or fluid. These include, for example, surfactants, masking agents, and perfumes to enhance customer appeal, and antifoaming agents to improve product manufacturing and use. These optional components can be used alone or in combination in the marker solution.

  Optional ingredients may be used in the range of about 0% to about 20% by weight of the reagent solution, in one embodiment about 0.01% to about 5% by weight, and in another embodiment about 0%. .1% to about 2% by weight.

Methods The invention includes: (1) adding an optional marker component to a fluid; (2) obtaining a fluid sample before, during, or after use of the fluid; (3) a polarized beam in the sample. Passing; (4) analyzing the result by measuring the rotation of the plane of polarized light after it has passed through the sample; and (5) determining and / or verifying the attributes of the fluid. A method for determining an attribute of a fluid. In some embodiments, the observed optical rotation is caused by the fluid itself without the addition of the optional optical markers described herein. In other embodiments, one or more of the optically active markers described above are added to the fluid, thereby causing at least some of the rotation observed in the fluid.

  In one embodiment, fluid is used in the application and the markers persist under the conditions of use so that fluid identification is further possible after such use. Such use includes the use of functional fluids such as lubricants in devices such as engines in operation. Includes exposure of fluids to extreme temperatures, extreme pressures, moving parts, and shear, or combinations thereof.

  It is not necessary to obtain a sample during actual operation of the engine or other device or machinery in order to obtain a representative sample of fluid. The fluid sample may be obtained at any time before, during, and / or after operation of the engine or apparatus or device. The fluid sample may be new, used, or a combination thereof. In one embodiment, fluid testing is particularly useful during and / or after operation for a period of time.

Diagnostic Kit The diagnostic kit includes means for generating a polarized beam and directing the light beam into a fluid sample. The kit further includes means for measuring the polarization beam and / or plane rotation after passing through the fluid sample as compared to the beam before passing through the sample. Measurement of the amount of rotation experienced by the plane of the polarized beam is a means for identifying the fluid under test.

  In one embodiment, the present invention excludes the use of reactive markers or reagents and the marker-containing sample of fluid reacts with the reagent to produce an observable response that is used for fluid identification.

  In one embodiment, the present invention excludes identification by observing compounds that are removed from the functional fluid by water extraction. Water extraction includes the case where compounds such as dyes in the functional fluid are removed from the functional fluid and withdrawn into the aqueous solution due to the miscibility of the compound in water. The observation of a compound that does not cause any reaction in aqueous solution is the only indicator provided.

  In one embodiment, the functional fluid is engine oil. Samples of engine oil, or other functional fluids to be tested, may be obtained using lubrication bars provided under lubrication as part of the engine, transmission, or other equipment. The user will withdraw a certain amount of oil along with a dipstick or other device, and then the oil into the sample container (if the sample container is glass or some other material that allows light to pass through) You may move on. The amount of fluid required to perform the test depends on the polarimeter used, and in some embodiments may be as little as a drop, or as high as several milliliters or hundreds of milliliters. . After placing the sample in the sample container, a polarized beam may be directed into the sample and a measurement of the rotation of the light beam may be observed. The user may refer to guides and / or visual markings to help interpret the observed rotation and to make decisions as fluid attributes, states, and / or sources.

  Fluid marking / identification is desirable because true fluid counterfeiting and falsification / dilution is a major challenge for fluid suppliers, and as a result of counterfeiting and falsification, loss of profits, customer dissatisfaction, brand name and This is because the reputation is harmed. A simple and easy-to-use marker system is beneficial because it can potentially make it impossible to distinguish between different fluids based on routine testing. Chemical analysis or physical properties can distinguish different fluids separately, but these analyzes require expensive laboratory test equipment and often time to do the actual end-user identification test. It takes too much. The disclosed method allows end users to efficiently and conveniently exclude products that have been counterfeited or tampered with based on optical rotation.

Visual Marking Analysis of the test sample can be accomplished by visual inspection of the light beam rotation and may include the provided visual marking as a guide.

  Visual markings may include artistic rendering, photo reconstruction of one or more functional fluids in various conditions with or without reagents. A visual indication is generally a representation of one or more functional fluids, two representations, or more than two representations, and / or a predicted light beam, rotation with respect to a fluid of a given source, It includes diagrams illustrating given attributes and / or given states. In one embodiment, the preferred visual indication is one or more expressions that indicate an accurate identification result and one or more expressions that indicate a negative identification result. An explanatory text corresponding to each of these examples can be shown. It will be appreciated that a different number of signs can be provided.

  The following data was collected on a JASCO model DIP-360 digital polarimeter operated according to the manufacturer's instructions. A 100 mm long test cell was used in all tests.

Example 1
Four fully formulated commercial engine oils are treated with several optically active markers and tested using a polarimeter. The results are summarized in the table below.

All reported test values marked with 1- ^* are the average of 2 to 5 results. All other reported values are the results of a single test. A blank indicates that no sample was prepared at that concentration level.
2-Oil A is unused Valvoline (trademark) motor oil. Oil B is unused Mobile 1 ™ oil. Oil C is a used Valveline ™ motor oil that was pulled from the car engine after 3700 miles. Oil D is Rotella ™ heavy vehicle engine oil.
The 3-marker is a mixture of D and L enantiomers with a slight excess of one enantiomer.

(Example 2)
Four fully formulated commercial functional fluids are treated with several optically active markers and tested using a polarimeter. The results are summarized in the table below.

All reported test values marked with 1- ^* are the average of 2 to 5 results. All other reported values are the results of a single test. A blank indicates that no sample was prepared at that concentration level.
2- Fluid A is an unused aromatic transmission fluid. Fluid B is a drain of used automatic transmission fluid after 155,000 miles. The fluid C is gear oil. The fluid D is a hydraulic fluid.
The 3-marker is a mixture of D and L enantiomers with a slight excess of one enantiomer.

Example 3
Two commercially available fuels are treated with several optically active markers and tested using a polarimeter. The results are summarized in the table below.

All reported test values marked with 1- ^* are the average of 2 to 5 results. All other reported values are the results of a single test. A blank indicates that no sample was prepared at that concentration level.
2- Fuel A is a commercially available diesel fuel. Fuel B is commercially available gasoline.
The 3-marker is a mixture of D and L enantiomers with a slight excess of one enantiomer.

  The results show that some fluids provide a measurable amount of optical rotation that may be used in the methods of the present invention as a means to identify and / or verify fluid attributes. The result is that the optically active markers defined above may be used in such fluids to adjust, influence and / or change the amount of optical rotation caused by the fluid. And the identification of the fluid can be made easier. Markers may be used to achieve an amount of rotation that would otherwise not be present with such fluids, thus providing a convenient means of identifying and / or verifying fluid attributes.

  Although the present invention has been described, it will be understood that various modifications thereof will become apparent to those skilled in the art upon reading this specification. Accordingly, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

  Each of the documents mentioned above is incorporated herein by reference. Except for the examples or where otherwise clearly indicated, all quantities in this specification that specify the amount of material, reaction conditions, molecular weight, number of carbon atoms, etc. are modified by the word about. Please understand that. Unless otherwise indicated, each chemical or composition referred to herein includes isomers, by-products, derivatives, and other materials normally understood to be present in commercial grade. It should be construed that it is a commercial grade material that may be included. However, the amount of each chemical component is indicated except for any solvent or diluent oil that may normally be present in the commercial material, unless otherwise indicated. Unless otherwise indicated, all percentage values are percent by weight. It should be understood that the upper and lower amount, range, and ratio limits set forth herein may be independently combined. Similarly, the ranges and amounts for each element of the invention can be used together with ranges or amounts for any of the other elements. As used herein, the expression “consisting essentially of” makes it possible to include substances that do not substantially affect the basic and novel characteristics of the composition under consideration.

Claims (1)

Invention described in this specification.